Method for producing antifouling film

ABSTRACT

The present invention provides a method for producing an antifouling film capable of long-term continuous production of an antifouling film having excellent antifouling properties. The method for producing an antifouling film of the present invention includes Process (1) of applying a resin to a surface of a substrate; Process (2) of applying a second release agent to a surface of a die coated with a first release agent; Process (3) of pushing the substrate to the surface of the die coated with the second release agent with the resin in between to form an uneven structure on a surface of the resin; and Process (4) of curing the resin including the uneven structure on the surface thereof to form a polymer layer. The resin contains an antifouling agent that contains a predetermined compound. The first release agent contains a predetermined compound. The second release agent contains a predetermined compound.

TECHNICAL FIELD

The present invention relates to methods for producing antifoulingfilms. The present invention more specifically relates to a method forproducing a film that includes an uneven structure of nanometer scaleand has antifouling properties.

BACKGROUND ART

Films including an uneven structure of nanometer scale (nanostructure)are known for their use as antireflection films (for example, see PatentLiteratures 1 and 2). This uneven structure has a continuously varyingrefractive index from the air layer to the substrate, thereby capable ofreducing the reflected light significantly.

CITATION LIST Patent Literature

Patent Literature 1: JP 2011-240546 A

Patent Literature 2: WO 2011/089836

SUMMARY OF INVENTION Technical Problem

Such films are usually produced using a die for forming an unevenstructure. In order to improve the releasability of the die, the surfaceof the die (the surface of the uneven structure) may be subjected torelease treatment with a release agent in some cases. Still,conventional production methods have difficulty in long-term continuousproduction of an antifouling film that includes on a surface thereof anuneven structure of nanometer scale and shows significant waterrepellency and oil repellency, i.e., significant antifouling properties.

The present inventors have studied to find that a die havinginsufficient releasability provides an antifouling film havinginsufficient antifouling properties. The present inventors examinedcauses of such insufficient releasability of the die to find that information of an uneven structure using the die, the die is brought intophysicochemical contact with a resin constituting the uneven structure,and thereby a release agent is removed from the die or the resindeposits (clogs) on the die. The present inventors therefore found thatlong-term continuous formation of an uneven structure with a die causesreduction of (a failure in keeping) releasability of the die.

As mentioned above, conventional methods for producing antifouling filmsneed to be improved in order to enable long-term continuous productionof an antifouling film having excellent antifouling properties.

Patent Literatures 1 and 2 disclose a structure in which a release agent(A) is applied to a die. The release agent (A) applied has highreactivity with a release agent (B) that has been applied to the die inadvance. Thus, the release agent (A) and the release agent (B) permeateinto the uneven structure and chemically bond to each other, and thereaction product fills the uneven structure. In this case, the reactionproduct filling the uneven structure is very difficult to remove,increasing the production cost. This means such a structure needs to beimproved in order to maintain the releasability of the die for a longtime.

The present invention is devised in view of the above state of the art,and aims to provide a method for producing an antifouling film capableof long-term continuous production of an antifouling film havingexcellent antifouling properties.

Solution to Problem

The present inventors performed various studies on a method forproducing an antifouling film capable of long-term continuous productionof an antifouling film having excellent antifouling properties, andfocused on prevention of physicochemical contact between a resinconstituting an uneven structure and a first release agent. The presentinventors then found a method in which a second release agent is appliedto a surface of a die coated with the first release agent, with thesecond release agent containing a predetermined compound that has lowreactivity with the first release agent. Finally, the present inventorshave arrived at an excellent solution to the above problems, completingthe present invention.

In other words, an aspect of the present invention may be a method forproducing an antifouling film including a polymer layer that includes ona surface thereof an uneven structure provided with multiple projectionsat a pitch not longer than a wavelength of visible light, the methodincluding: Process (1) of applying a resin to a surface of a substrate;Process (2) of applying a second release agent to a surface of a diecoated with a first release agent; Process (3) of pushing the substrateto the surface of the die coated with the second release agent with theresin in between to form the uneven structure on a surface of the resin;and Process (4) of curing the resin including the uneven structure onthe surface thereof to form the polymer layer, the resin containing anantifouling agent that contains a compound containing aperfluoro(poly)ether group, the first release agent containing acompound that contains a perfluoro(poly)ether group, a hydrolyzablegroup, and a Si atom, the second release agent containing a compoundrepresented by the following formula (F):R¹¹¹—(R¹¹²O)_(m)—R¹¹³  (F)wherein R¹¹¹ and R¹¹³ are each individually a fluorine atom or a —OHgroup; R¹¹² is a C1-C4 fluorinated alkylene group; and m is an integerof 2 or greater.

Advantageous Effects of Invention

The present invention can provide a method for producing an antifoulingfilm capable of long-term continuous production of an antifouling filmhaving excellent antifouling properties.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1-1 includes schematic cross-sectional views illustrating a methodfor producing an antifouling film of an embodiment (a to c).

FIG. 1-2 includes schematic cross-sectional views illustrating themethod for producing an antifouling film of the embodiment (d and e).

FIG. 2 is a graph showing the results of measuring the reflectances ofan antifouling film (1 time) and an antifouling film (20 times) ofExample 1.

FIG. 3 is a graph showing the results of measuring the reflectances ofan antifouling film (1 time) and an antifouling film (20 times) ofExample 2.

FIG. 4 is a graph showing the results of measuring the reflectances ofan antifouling film (1 time) and an antifouling film (20 times) ofComparative Example 1.

FIG. 5 is a graph showing the transition of the contact angles of wateron dies used in Comparative Examples 6 to 9.

FIG. 6 is a graph showing the transition of the reflectances of anantifouling film of Comparative Example 6.

DESCRIPTION OF EMBODIMENTS

Hereinafter, the present invention is described in more detail based onan embodiment with reference to the drawings. The embodiment, however,is not intended to limit the scope of the present invention. Thefeatures of the embodiment may appropriately be combined or modifiedwithin the spirit of the present invention.

The expression “A to B” as used herein means “not lower than A and notgreater than B”.

The antifouling film as used herein means a film that enables easyremoval of dirt sticking to a surface thereof.

The active hydrogen as used herein means a hydrogen atom that can begiven as a proton to an isocyanate group.

The active-hydrogen-containing group as used herein means a groupcontaining active hydrogen, and examples thereof include a —OH group, a—C(═O)H group, a —SH group, a —SO₃H group, a —SO₂H group, a —SOH group,a —NH₂ group, a —NH— group, and a —SiH group.

The divalent organic group as used herein means a divalent groupcontaining carbon. The divalent organic group may be, but is not limitedto, a divalent group obtained by removing another hydrogen atom from ahydrocarbon group.

The hydrocarbon group as used herein means a group containing carbon andhydrogen. Examples of the hydrocarbon group include, but are not limitedto, C1-C20 hydrocarbon groups optionally substituted with one or moresubstituents, such as aliphatic hydrocarbon groups and aromatichydrocarbon groups. Each aliphatic hydrocarbon group may be linear,branched, or cyclic, and may be either saturated or unsaturated. Thehydrocarbon group may contain one or more cyclic structure. Thehydrocarbon group may contain, at an end or in the molecular chainthereof, one or more of atoms and groups such as N, O, S, Si, amide,sulfonyl, siloxane, carbonyl, and carbonyloxy.

Examples of the substituents for the hydrocarbon group as used hereininclude, but are not limited to, C1-C6 alkyl groups, C2-C6 alkenylgroups, C2-C6 alkynyl groups, C3-C10 cycloalkyl groups, C3-C10unsaturated cycloalkyl groups, 5- to 10-membered heterocyclyl groups, 5-to 10-membered unsaturated heterocyclyl groups, C6-C10 aryl groups, and5- to 10-membered heteroaryl groups, optionally substituted with one ormore halogen atoms.

The hydrolyzable group as used herein means a group that can be desorbedfrom the main backbone of a compound by hydrolysis. The hydrolyzablegroup may be an alkoxy group. Specific examples thereof include —OA,—OCOA, —O—N═C(A)₂, —N(A)₂, —NHA, and halogens, wherein A is asubstituted or non-substituted C1-C3 alkyl group.

The number average molecular weight as used herein means a valuedetermined by ¹⁹F-NMR.

[Embodiment]

A method for producing an antifouling film of an embodiment is describedbelow with reference to FIG. 1-1 and FIG. 1-2. FIG. 1-1 includesschematic cross-sectional views illustrating a method for producing anantifouling film of the embodiment (a to c). FIG. 1-2 includes schematiccross-sectional views illustrating the method for producing anantifouling film of the embodiment (d and e).

(a) Application of Resin (Process (1))

As shown in FIG. 1-1(a), a resin 3 is applied to a surface of asubstrate 2. Separately, a die 4 is prepared. A surface of the die 4 iscoated with a first release agent 5 (has undergone release treatment).

Examples of a technique of applying the resin 3 include spray coating,gravure coating, and slot-die coating. In order to easily adjust thefilm thickness and to reduce the device cost, gravure coating orslot-die coating is preferred.

(b) Application of Second Release Agent (Process (2))

As shown in FIG. 1-1(b), a second release agent 8 is applied to thesurface of the die 4 coated with the first release agent 5. Thereby, thesecond release agent 8 is placed on the first release agent 5 on theside opposite to the die 4.

Examples of a technique of applying the second release agent 8 includetechniques similar to those for applying the resin 3 as mentioned aboveand potting.

The application of the resin 3 (Process (1)) and the application of thesecond release agent 8 (Process (2)) may be performed eithernon-simultaneously or simultaneously. The application of the secondrelease agent 8 may not be performed every time the uneven structure isformed, but may be performed intermittently as long as the resin 3 andthe first release agent 5 are prevented from being in contact with eachother.

(c) Formation of Uneven Structure (Process (3))

As shown in FIG. 1-1(c), the substrate 2 is pushed to the surface of thedie 4 coated with the second release agent 8 with the resin 3 inbetween. As a result, the uneven structure is formed on a surface (asurface opposite to the substrate 2) of the resin 3.

(d) Curing of Resin (Process (4))

As shown in FIG. 1-2(d), the resin 3 including the uneven structure onthe surface thereof is cured, so that a polymer layer 6 is formed.

Examples of the method of curing the resin 3 include application ofactive energy rays and heating, and a method utilizing application ofactive energy rays is preferred. The active energy rays herein meanultraviolet rays, visible light, infrared rays, plasma, or the like. Theresin 3 is preferably one that is curable by ultraviolet rays.Application of active energy rays to the resin 3 may be performed fromthe substrate 2 side of the resin 3, or may be performed from the die 4side of the resin 3. Application of active energy rays to the resin 3may be performed once or may be performed multiple times. Curing of theresin 3 may be performed simultaneously with the aforementionedformation of the uneven structure on the resin 3.

(e) Release of Die

As shown in FIG. 1-2(e), the die 4 is released from the polymer layer 6.As a result, an antifouling film 1 is completed. The uneven structureformed on the surface (the surface opposite to the substrate 2) of thepolymer layer 6 corresponds to a structure provided with multipleprojections (protrusions) 7 at a pitch (distance between the apexes ofadjacent projections 7) P not longer than the wavelength of visiblelight, i.e., a moth-eye structure (a structure like a moth's eye). Thus,the antifouling film 1 can exert excellent antireflective properties(low reflectivity) owing to the moth-eye structure. The antifouling film1 may be applied to any use that utilizes the excellent antifoulingproperties thereof, and the use is not limited to an optical film suchas an antireflection film.

In the aforementioned production process, Processes (1) to (4) can becontinuously and efficiently performed if the substrate 2 is in the formof a roll.

Next, the materials used in production of the antifouling film 1 aredescribed below.

The material of the substrate 2 may be, for example, a resin such astriacetyl cellulose (TAC), polyethylene terephthalate (PET), polymethylmethacrylate (PMMA), a cycloolefin polymer (COP), or polycarbonate (PC),and may be selected as appropriate in accordance with the useenvironment. These materials can provide a substrate 2 having highhardness and excellent transparency and weather resistance. One surface(the surface close to the polymer layer 6) of the substrate 2 may haveundergone easy adhesion treatment. For example, a triacetyl cellulosefilm with easy adhesion treatment may be used. One surface (the surfaceclose to the polymer layer 6) of the substrate 2 may have undergonesaponification treatment. For example, a saponified triacetyl cellulosefilm may be used. The resin to be used as a material of the substrate 2may be colored. The material of the substrate 2 is not limited to theabove resins, and may be glass, metal, fiber, or paper (includingprinted matter such as a photograph), for example.

In order to ensure the transparency and processability, the substrate 2preferably has a thickness of 20 μm or greater and 200 μm or smaller,more preferably 40 μm or greater and 100 μm or smaller.

The resin 3 contains an antifouling agent that contains a compoundcontaining a perfluoro(poly)ether group.

The antifouling agent preferably contains a compound that contains aperfluoro(poly)ether group and a curable moiety (e.g., an acrylategroup). Specifically, the antifouling agent preferably contains acarbon-carbon double bond-containing compound (perfluoropolyethercompound) that is a reaction product of a component (A) and a component(B), the component (A) being a polyisocyanate that is a trimer of adiisocyanate and the component (B) being an active-hydrogen-containingcompound.

The component (A) is a polyisocyanate obtainable by trimerizing adiisocyanate. The polyisocyanate which is a trimer of a diisocyanate maybe present in the form of a polymer thereof.

The component (A), i.e., a polyisocyanate that is a trimer of adiisocyanate, may preferably be an isocyanurate-type polyisocyanate. Theisocyanurate-type polyisocyanate may be present in the form of a polymerthereof. In other words, the isocyanurate-type polyisocyanate may be amonocyclic compound containing only one isocyanurate ring, or apolycyclic compound obtained by polymerizing this monocyclic compound,or a mixture thereof. A known example of the isocyanurate-typepolyisocyanate is “Sumidur® N3300” (Sumika Bayer Urethane Co., Ltd.).

Examples of the diisocyanate to be used for producing the component (A),i.e., a polyisocyanate that is a trimer of a diisocyanate, include, butare not limited to, diisocyanates in which an isocyanate group binds toan aliphatic group, such as hexamethylene diisocyanate, isophoronediisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate,and dicyclohexylmethane diisocyanate; and diisocyanates in which anisocyanate group binds to an aromatic group, such as tolylenediisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylpolyisocyanate, tolidine diisocyanate, and naphthalene diisocyanate.

Examples of the component (A), i.e., a polyisocyanate that is a trimerof a diisocyanate, include, but are not limited to, compounds having astructure represented by the following formula (D6), (D7), (D8), or(D9).

As mentioned above, these polyisocyanates may be present in the form ofa polymer. For example, an isocyanurate-type polyisocyanate ofhexamethylene diisocyanate may be present in the form of a polymerhaving a structure represented by the following formula (D10).

The component (B) contains a component (B1) that is anactive-hydrogen-containing perfluoropolyether and a component (B2) thatis a monomer containing a carbon-carbon double bond-containing group andactive hydrogen.

The component (B1) is at least one compound represented by one of thefollowing formulas (B1-i) and (B1-ii). The component (B1) can improvethe antifouling properties and the rubbing resistance (smoothness) ofthe antifouling film 1.Rf-PFPE¹-Z—X  (B1-i)X—Z-PFPE²-Z—X  (B1-ii)

In the formulas (B1-i) and (B1-ii), Rf is a C1-C16 (e.g., linear orbranched) alkyl group optionally substituted with one or more fluorineatoms, preferably a C1-C3 linear or branched alkyl group optionallysubstituted with one or more fluorine atoms. Rf is preferably linear.The alkyl group optionally substituted with one or more fluorine atomsis preferably a fluoroalkyl group in which the terminal carbon atoms areCF₂H— and the other carbon atoms are substituted with a fluorine atom,or a perfluoroalkyl group, more preferably a perfluoroalkyl group,specifically —CF₃, —CF₂CF₃, or —CF₂CF₂CF₃.

In the formulas (B1-i) and (B1-ii), PFPE¹ is a group represented by thefollowing formula (D1), (D2), or (D3):—(OCF₂CF₂CF₂CF₂)_(b)—  (D1)wherein b is an integer of 1 to 200, preferably an integer of 5 to 200,more preferably an integer of 10 to 200;—(OCF₂CF₂CF₂CF₂)_(a)—(OCF₂CF₂CF₂CF₂)_(b)—(OCF₂CF₂)_(c)—(OCF₂)_(d)—  (D2)wherein a and b are each individually an integer of 0 to 30; c and d areeach individually an integer of 1 to 200, preferably an integer of 5 to200, more preferably an integer of 10 to 200; and the repeating unitsparenthesized with a, b, c, or d are present in any order in the formula(D2); and—(OC₂F₄—R⁵)_(i)—  (D3)wherein R⁵ is OC₂F₄, OC₃F₆, or OC₄F₈; and i is an integer of 2 to 100,preferably an integer of 2 to 50.

In an embodiment, in the formulas (B1-i) and (B1-ii), PFPE¹ may be agroup represented by the formula (D1) or (D3), and is preferably a grouprepresented by the formula (D1). The presence of such PFPE¹ can furtherimprove the antifouling properties of the antifouling film 1.

In the formulas (B1-i) and (B1-ii), PFPE² is a group represented by thefollowing formula (D4) or (D5), and is preferably a group represented bythe following formula (D4):—(OCF₂CF₂CF₂CF₂)_(b)—  (D4)wherein b is an integer of 1 to 200, preferably an integer of 5 to 200,more preferably an integer of 10 to 200; and—(OC₂F₄—R⁵)_(i)—  (D5)wherein R⁵ is OC₂F₄, OC₃F₆, or OC₄F₈; and i is an integer of 2 to 100,preferably an integer of 2 to 50.

In the formulas (B1-i) and (B1-ii), Zs are each individually a divalentorganic group; each Z is preferably R¹; and R¹s are each individually agroup represented by the following formula (D11).—(Y)_(f)—(CR³ ₂)_(j)—  (D11)

In the formula (D11), Y is a divalent polar group. Examples of thedivalent polar group include, but are not limited to, —COO—, —OCO—,—CONH—, —OCH₂CH(OH)CH₂—, —CH₂CH(OH)CH₂O—, —COS—, —SCO—, and —O—.Preferred is —COO—, —CONH—, —CH₂CH(OH)CH₂O—, or —O—.

In the formula (D11), R³s are each individually a hydrogen atom or afluorine atom.

In the formula (D11), f is an integer of 0 to 50, preferably an integerof 0 to 20 (e.g., an integer of 1 to 20); j is an integer of 0 to 100,preferably an integer of 0 to 40 (e.g., an integer of 1 to 40); the sumof f and j is 1 or greater; and the repeating units parenthesized with for j are present in any order in the formula (D11).

R¹s represented by the formula (D11) are preferably each individually agroup represented by the following formula (D12).—(Y)_(f)—(CF₂)_(g)—(CH₂)_(h)—  (D12)

In the formula (D12), Y and f are respectively defined in the samemanner as Y and f in the formula (D11); g and h are each individually aninteger of 0 to 50, preferably an integer of 0 to 20 (e.g., an integerof 1 to 20); the sum of f, g, and h is 1 or greater, preferably 1 to 10;f, g, and h are each more preferably an integer of 0 to 2, still morepreferably f=0 or 1, g=2, and h=0 or 1; and the repeating unitsparenthesized with f, g, or h are present in any order in the formula(D12).

In the formulas (B1-i) and (B1-ii), X is an active-hydrogen-containinggroup. Xs are preferably each individually a —OH group, a —C(═O)H group,a —SH group, a —SO₃H group, a —SO₂H group, a —SOH group, a —NH₂ group, a—NH— group, or a —SiH group, more preferably a —OH group or a —NH₂group, still more preferably a —OH group.

The component (B1) is preferably at least one compound represented byone of the following formulas (B1-i′) and (B1-ii′), more preferably atleast one compound represented by the following formula (B1-i′). In thecomponent (B1) which is at least one compound represented by thefollowing formula (B1-i′), PFPE¹ is preferably a group represented bythe formula (D1). The compound represented by the following formula(B1-i′) can further improve the rubbing resistance of the antifoulingfilm 1.Rf-PFPE¹-R¹—CH₂OH  (B1-i′)HOCH₂—R¹—PFPE²-R¹—CH₂OH  (B1-ii′)

In the formulas (B1-i′) and (B1-ii′), Rf, PFPE¹, and PFPE² arerespectively defined in the same manner as Rf, PFPE¹, and PFPE² in theformulas (B1-i) and (B1-ii). In the formulas (B1-i′) and (B1-ii′), R¹ isdefined in the same manner as R¹ represented by the formula (D11).

The component (B1), i.e., an active-hydrogen-containingperfluoropolyether, is a compound containing oneactive-hydrogen-containing group (e.g., a hydroxy group) at onemolecular end or one active-hydrogen-containing hydroxy group at each oftwo molecular ends in addition to the perfluoropolyether group. Thecompound containing a perfluoropolyether group can improve theantifouling properties (e.g., water repellency, oil repellency, ease ofwiping of fingerprints) of the antifouling film 1.

The component (B1), i.e., an active-hydrogen-containingperfluoropolyether, preferably has a number average molecular weight of,although not limited to, 500 to 12000, more preferably 1000 to 10000,still more preferably 1500 to 8000.

The component (B2), i.e., a monomer containing a carbon-carbon doublebond-containing group and active hydrogen, contains at least one(preferably one) active-hydrogen-containing group (preferably a hydroxygroup) at a molecular end thereof.

The component (B2), i.e., a monomer containing a carbon-carbon doublebond-containing group and active hydrogen, preferably contains a grouprepresented by the following formula (D13) as a carbon-carbon doublebond-containing group.—OC(O)—CR²═CH₂  (D13)

In the formula (D13), R² is a hydrogen atom, a chlorine atom, a fluorineatom, or a C1-C10 alkyl group optionally substituted with a fluorineatom, preferably a hydrogen atom or a C1-C3 alkyl group, more preferablya hydrogen atom or a methyl group. The groups in which R² is a hydrogenatom or a methyl group, i.e., —OC(O)—CH═CH₂ and —OC(O)—CCH₃═CH₂ are alsocollectively referred to as “(meth)acrylate groups”.

Examples of the component (B2) include, but are not limited to, thefollowing compounds:HO(CH₂CH₂)_(i)OCO(R)C═CH₂  (D14)(wherein R is a hydrogen atom, a chlorine atom, a fluorine atom, or aC1-C10 alkyl group optionally substituted with a fluorine atom; and i isan integer of 2 to 10), such as 2-hydroxyethyl (meth)acrylate and4-hydroxybutyl (meth)acrylate;CH₃CH(OH)CH₂OCO(R)C═CH₂  (D15)(wherein R is a hydrogen atom, a chlorine atom, a fluorine atom, or aC1-C10 alkyl group optionally substituted with a fluorine atom), such as2-hydroxypropyl (meth)acrylate;CH₃CH₂CH(OH)CH₂OCO(R)C═CH₂  (D16)(wherein R is a hydrogen atom, a chlorine atom, a fluorine atom, or aC1-C10 alkyl group optionally substituted with a fluorine atom), such as2-hydroxybutyl (meth)acrylate;C₆H₅OCH₂CH(OH)CH₂OCO(R)C═CH₂  (D17)(wherein R is a hydrogen atom, a chlorine atom, a fluorine atom, or aC1-C10 alkyl group optionally substituted with a fluorine atom), such as2-hydroxy-3-phenoxypropyl (meth)acrylate;HOCH₂C(CH₂OCO(R)C═CH₂)₃  (D18)(wherein R is a hydrogen atom, a chlorine atom, a fluorine atom, or aC1-C10 alkyl group optionally substituted with a fluorine atom), such aspentaerythritol triacrylate;C(CH₂OCO(R)C═CH₂)₃CH₂OCH₂C(CH₂OCO(R)C═CH₂)₂CH₂OH  (D19)(wherein R is a hydrogen atom, a chlorine atom, a fluorine atom, or aC1-C10 alkyl group optionally substituted with a fluorine atom), such asdipentaerythritol polyacrylate;HOCH₂CH₂OCOC₆H₅OCOCH₂CH₂OCO(R)C═CH₂  (D20)(wherein R is a hydrogen atom, a chlorine atom, a fluorine atom, or aC1-C10 alkyl group optionally substituted with a fluorine atom), such as2-acryloyloxyethyl-2-hydroxyethyl phthalate;H(OCH₂CH₂)_(n)OCO(R)C═CH₂  (D21)(wherein R is a hydrogen atom, a chlorine atom, a fluorine atom, or aC1-C10 alkyl group optionally substituted with a fluorine atom; and n isan integer of 1 to 30), such as poly(ethylene glycol) acrylate;H(OCH(CH₃)CH₂)_(n)OCO(R)C═CH₂  (D22)(wherein R is a hydrogen atom, a chlorine atom, a fluorine atom, or aC1-C10 alkyl group optionally substituted with a fluorine atom; and n isan integer of 1 to 30), such as poly(propylene glycol) acrylate;

-   -   allylalcohol;        HO(CH₂)_(k)CH═CH₂  (D23)        (wherein k is an integer of 2 to 20);    -   (CH₃)₃SiCH(OH)CH═CH₂; and    -   styrylphenols.

In an embodiment, the component (B) may contain a component (B1) and acomponent (B2).

The carbon-carbon double bond-containing compound contained in theantifouling agent may contain groups derived from different components(B1) in one triisocyanate molecule. Also, this compound may containgroups derived from different components (B2) (e.g., containingdifferent numbers of carbon-carbon double bonds) in one triisocyanatemolecule.

The antifouling agent may contain one or more carbon-carbon doublebond-containing compounds. For example, the antifouling agent may be amixture of a compound obtained by reacting the component (A), a compoundB1 as the component (B1), and a compound B2 as the component (B2), and acompound obtained by reacting the component (A), a compound B1′ as thecomponent (B1), and a compound B2′ as the component (B2). Thesecompounds may be synthesized simultaneously, or may be synthesizedseparately and then mixed with each other.

Examples of known antifouling agents include “Optool® DAC” and “OptoolDAC-HP” (Daikin Industries, Ltd.), “KY-1203” and “KNS5300” (Shin-EtsuChemical Co., Ltd.), “Megaface® RS-75”, “Megaface RS-72-K”, “MegafaceRS-76-E”, “Megaface RS-76-NS”, “Megaface RS-90”, “Defensa® TF3028”,“Defensa TF3001”, and “Defensa TF3000” (DIC Corp.), “SUA1900L10” and“SUA1900L6” (Shin Nakamura Chemical Co., Ltd.), and “Fluorolink® P56”,“Fluorolink P54”, “Fluorolink F10”, “Fluorolink A10P”, “FluorolinkAD1700”, “Fluorolink MD700”, and “Fluorolink E10H” (Solvay).

The resin 3 preferably contains 0.1 to 10 wt %, more preferably 0.5 to 5wt %, of an active component of the antifouling agent. Less than 0.1 wt% of the active component of the antifouling agent in the resin 3 maycause too small an amount of the active component of the antifoulingagent on the surface (the surface opposite to the substrate 2) of thepolymer layer 6. This may cause insufficient antifouling properties andpoor rubbing resistance. More than 10 wt % of the active component ofthe antifouling agent in the resin 3 may cause too large an amount ofthe active component of the antifouling agent on the surface (thesurface opposite to the substrate 2) of the polymer layer 6. This maycause poor elasticity of the polymer layer 6 (projections 7), and theprojections 7 fallen by rubbing the surface (the surface opposite to thesubstrate 2) of the polymer layer 6 may be less likely to rise (restore)again. As a result, the rubbing resistance may be poor.

The resin 3 may further contain a compatibilizer that is compatible withthe above antifouling agent. The compatibilizer can prevent occurrenceof cloudiness even when the resin 3 contains a large amount of theantifouling agent.

Examples of the compatibilizer include N-acryloylmorpholine (e.g.,“ACMO®” (KJ Chemicals Corp.)), N,N-diethylacrylamide (e.g., “DEAA®” (KJChemicals Corp.)), N,N-dimethylacrylamide (e.g., “DMAA®” (KJ ChemicalsCorp.)), tetrahydrofurfuryl acrylate (e.g., “Viscoat #150” (OsakaOrganic Chemical Industry Ltd.)), cyclic trimethylolpropane formalacrylate (e.g., “Viscoat #200” (Osaka Organic Chemical Industry Ltd.)),4-hydroxybutyl (meth)acrylate (e.g., “4HBA” (Nippon Kasei Chemical Co.,Ltd.)), phenoxyethyl acrylate, benzyl acrylate, stearyl acrylate, laurylacrylate, 2-ethylhexyl acrylate, allyl acrylate, 1,3-butanedioldiacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate,pentaerythritol triacrylate, dipentaerythritol hexaacrylate, glycidylacrylate, diethylene glycol diacrylate, polyoxyethylene glycoldiacrylate, tripropylene glycol diacrylate, 2-hydroxyethyl acrylate,4-hydroxybutylvinyl ether, N,N-dimethylaminoethyl acrylate,N-vinylpyrrolidone, dimethylaminoethyl (meth)acrylate, silicone-basedacrylates, 2,2,3,3-tetrafluoropropyl (meth)acrylate,2,2,3,3,4,4,5,5-octafluoropropyl (meth)acrylate, methyl (meth)acrylate,ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate,n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl(meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate,3-methylbutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethyl-n-hexyl(meth)acrylate, n-octyl (meth)acrylate, cyclohexyl (meth)acrylate,isobornyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl(meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl(meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, neopentylglycolmono(meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate,(1,1-dimethyl-3-oxobutyl) (meth)acrylate, 2-acetoacetoxyethyl(meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl(meth)acrylate, neopentylglycol mono(meth)acrylate,3-chloro-2-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate,ethylene glycol diacrylate, propylene glycol diacrylate, 1,6-hexanedioldiacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate,trimethylolpropane triacrylate, and pentaerythritol tetraacrylate. Thecompatibilizer is preferably a monofunctional monomer containing a polargroup such as an amide group, an ether group, or a hydroxy group. In theresin 3, the compatibilizer may be contained in the antifouling agent,or in a component other than the antifouling agent, or in both of them.

The resin 3 preferably contains 10 to 40 wt %, more preferably 20 to 30wt %, of the compatibilizer. Less than 10 wt % of the compatibilizer inthe resin 3 may cause poor solubility of the antifouling agent in thecompatibilizer. More than 40 wt % of the compatibilizer in the resin 3may soften the polymer layer 6, reducing the elasticity. This may resultin poor rubbing resistance of the antifouling film 1.

The resin 3 used may include one or two or more curable resins, one ortwo or more curable monomers, or a mixture of a curable resin and acurable monomer.

The curable resin may be any resin having heat resistance and sufficientstrength, and may be any of a photo-curable resin and a thermosettingresin. An ultraviolet-curable resin is more preferred.

Examples of the curable resin include acrylic polymers, polycarbonatepolymers, polyester polymers, polyamide polymers, polyimide polymers,polyethersulfone polymers, cyclic polyolefin polymers,fluorine-containing polyolefin polymers (e.g., PTFE), andfluorine-containing cyclic amorphous polymers. In the case of performinga treatment such as curing by ultraviolet irradiation after theformation of an uneven structure (the above Process (3)), the curableresin is preferably a resin having transparency.

Specific examples of the curable resin include alkyl vinyl ethers suchas cyclohexyl methyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinylether, and ethyl vinyl ether, glycidyl vinyl ether, vinyl acetate, vinylpivalate, (meth)acrylates such as phenoxyethyl acrylate, benzylacrylate, stearyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate,allyl acrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate,1,6-hexanediol diacrylate, trimethylolpropane triacrylate,pentaerythritol triacrylate, dipentaerythritol hexaacrylate, ethoxyethylacrylate, methoxyethyl acrylate, glycidyl acrylate, tetrahydrofurfurylacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate,polyoxyethylene glycol diacrylate, tripropylene glycol diacrylate,2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, N,N-diethylaminoethylacrylate, N,N-dimethylaminoethyl acrylate, dimethylaminoethylmethacrylate, and silicone-based acrylates, 4-hydroxybutyl vinyl ether,N-vinylpyrrolidone, maleic anhydride, vinylene carbonate, chainlike sidechain polyacrylates, cyclic side chain polyacrylates, polynorbornene,polynorbornadiene, polycarbonate, polysulfonamide, andfluorine-containing cyclic amorphous polymers (e.g., Cytop®, Teflon®AF).

The curable monomer may be either a photo-curable monomer or athermosetting monomer, and is preferably an ultraviolet-curable monomer.

Examples of the curable monomer include (a) urethane (meth)acrylates,(b) epoxy (meth)acrylates, (c) polyester (meth)acrylates, (d) polyether(meth)acrylates, (e) silicone (meth)acrylates, and (f) (meth)acrylatemonomers.

Specific examples of the curable monomer include the following.

The urethane (meth)acrylates (a) are those containing a urethane bondand a (meth)acryloyl group in a molecule. Examples of the urethane(meth)acrylates (a) include poly((meth)acryloyloxyalkyl)isocyanuratestypified by tris(2-hydroxyethyl)isocyanurate diacrylate andtris(2-hydroxyethyl)isocyanurate triacrylate.

The epoxy (meth)acrylates (b) are obtained by adding a (meth)acryloylgroup to an epoxy group, typified by those obtained from a startingmaterial such as bisphenol A, bisphenol F, phenol novolac, or analicyclic compound.

The polyester (meth)acrylates (c) may be ester resins containing apolyhydric alcohol and a polybasic acid with a (meth)acrylate addedthereto. Examples of the polyhydric alcohol include ethylene glycol,1,4-butanediol, 1,6-hexanediol, diethylene glycol, trimethylolpropane,dipropylene glycol, polyethylene glycol, polypropylene glycol,pentaerythritol, and dipentaerythritol. Examples of the polybasic acidinclude phthalic acid, adipic acid, maleic acid, trimellitic acid,itaconic acid, succinic acid, terephthalic acid, and alkenylsuccinicacid.

The polyether (meth)acrylates (d) are polyether resins of a diol with a(meth)acrylate added thereto. Examples of the polyether (meth)acrylates(d) include polyethylene glycol di(meth)acrylate, polypropylene glycoldi(meth)acrylate, and polyethylene glycol-polypropylene glycoldi(meth)acrylate.

The silicone (meth)acrylates (e) are those obtained by modifying atleast one end of dimethyl polysiloxane having a molecular weight of 1000to 10000 with a (meth)acryloyl group, and examples thereof includecompounds represented by the following formula (D24), (D25), or (D26).

The (meth)acrylate monomers (f) are monofunctional or multifunctionalalkyl (meth)acrylates or polyether (meth)acrylates having a lowviscosity of 500 mPa·s or lower (25° C.). Examples of the (meth)acrylatemonomers (f) include methyl (meth)acrylate, ethyl (meth)acrylate,n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl(meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate,t-butyl (meth)acrylate, n-pentyl (meth)acrylate, 3-methylbutyl(meth)acrylate, n-hexyl (meth)acrylate, 2-ethyl-n-hexyl (meth)acrylate,n-octyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl(meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate,2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate,4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate,6-hydroxyhexyl (meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate,neopentyl glycol mono(meth)acrylate, 3-chloro-2-hydroxypropyl(meth)acrylate, (1,1-dimethyl-3-oxobutyl) (meth)acrylate,2-acetoacetoxyethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate,2-ethoxyethyl (meth)acrylate, neopentyl glycol mono(meth)acrylate,3-chloro-2-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate,ethylene glycol diacrylate, propylene glycol diacrylate, 1,6-hexanedioldiacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate,trimethylolpropane triacrylate, and pentaerythritol tetraacrylate.

Preferred examples of known curable resins and curable monomers are asfollows.

Examples of the curable resins include silicone resins (e.g., “PAK-01”and “PAK-02”, Toyo Gosei Co., Ltd.); nanoimprint resins (e.g., “NIF”series, Asahi Glass Co., Ltd.; “OCNL” series, Tokyo Ohka Kogyo Co.,Ltd.; and “NIAC2310”, Daicel Chemical Industries, Co., Ltd.); epoxyacrylate resins (e.g., “EH-1001”, “ES-4004”, “EX-C101”, “EX-C106”,“EX-C300”, “EX-C501”, “EX-0202”, “EX-0205”, and “EX-5000”, KyoeishaChemical Co., Ltd.); and hexamethylene diisocyanate-basedpolyisocyanates and isocyanurate-type polyisocyanates (e.g., “SumidurN-75”, “Sumidur N3200”, “Sumidur HT”, “Sumidur N3300”, and “SumidurN3500”, Sumika Bayer Urethane Co., Ltd.).

Examples of the silicone acrylate resins among the curable monomersinclude: “Silaplane® FM-0611”, “Silaplane FM-0621”, and “SilaplaneFM-0625”; bi-terminal-type (meth)acrylate resins such as “SilaplaneFM-7711”, “Silaplane FM-7721”, and “Silaplane FM-7725”; “SilaplaneFM-0411”, “Silaplane FM-0421”, “Silaplane FM-0428”, “Silaplane FM-DA11”,“Silaplane FM-DA21”, and “Silaplane DA25”; mono-terminal-type(meth)acrylate resins such as “Silaplane FM-0711”, “Silaplane FM-0721”,“Silaplane FM-0725”, “Silaplane TM-0701”, and “Silaplane TM-0701T” (JNCCo., Ltd.).

Examples of the multifunctional acrylates among the curable monomersinclude “U-10HA”, “U-10PA”, “UA-33H”, “UA-53H”, “UA-1100H”, “UA-7000”,“UA-7100”, “ATM-4E”, “ATM-35E”, “A-DPH”, “A-9300”, “A-9300-1CL”,“A-GLY-9E”, “A-GLY-20E”, “A-TMM-3”, “A-TMM-3L”, “A-TMM-3LM-N”, “A-TMPT”,and “A-TMMT” (Shin-Nakamura Chemical Co., Ltd.); “UA-306H”, “UA-53T”,“UA-510H”, “Light Acrylate PE-3A”, and “Light Acrylate DPE-6A” (KyoeishaChemical Co., Ltd.); and “PET-3” (DKS Co., Ltd.).

An example of the multifunctional methacrylates among the curablemonomers is “TMPT” (Shin-Nakamura Chemical Co., Ltd.).

Examples of the alkoxysilane group-containing (meth)acrylates among thecurable monomers include 3-(meth)acryloyloxypropyltrichlorosilane,3-(meth)acryloyloxypropyltrimethoxysilane,3-(meth)acryloyloxypropyltriethoxysilane,3-(meth)acryloyloxypropyltriisopropoxysilane (also referred to as(triisopropoxysilyl)propyl methacrylate (abbreviation: TISMA) and(triisopropoxysilyl)propyl acrylate),3-(meth)acryloxyisobutyltrichlorosilane,3-(meth)acryloxyisobutyltriethoxysilane,3-(meth)acryloxyisobutyltriisopropoxysilane, and3-(meth)acryloxyisobutyltrimethoxysilane.

The amount of the curable resin or the curable monomer is preferably 5to 99 parts by mass, more preferably 10 to 99 parts by mass, still morepreferably 50 to 99 parts by mass, with the whole amount of the resin 3taken as 100 parts by mass. The curable resin or monomer in such anamount can lead to a uniform composition without phase separation.

The resin 3 may further contain a crosslinking catalyst. Examples of thecrosslinking catalyst include polymerization initiators and acidgenerators.

Examples of the polymerization initiators include radical polymerizationinitiators, anionic polymerization initiators, and cationicpolymerization initiators. The resin 3 may contain one or multiple ofthese polymerization initiators.

The radical polymerization initiators are compounds that generate aradical by application of heat or light, for example. Examples of theradical polymerization initiators include radical thermal polymerizationinitiators and radical photo-polymerization initiators.

Examples of the radical thermal polymerization initiators include:peroxide compounds, including diacyl peroxides such as benzoyl peroxideand lauroyl peroxide, dialkyl peroxides such as dicumyl peroxide anddi-t-butyl peroxide, peroxy carbonates such as diisopropylperoxydicarbonate and bis(4-t-butylcyclohexyl)peroxydicarbonate, andalkyl peresters such as t-butyl peroxyoctoate and t-butylperoxybenzoate; and radical-generating azo compounds such asazobisisobutyronitrile.

Examples of the radical photo-polymerization initiators include:-diketones such as benzyl and diacetyl; acyloins such as benzoin;acyloin ethers such as benzoin methyl ether, benzoin ethyl ether,benzoin propyl ether, benzoin isobutyl ether, and benzoin isopropylether; thioxanthones such as thioxanthone, 2,4-diethyl thioxanthone,2-isopropyl thioxanthone, 2-chlorothioxanthone, andthioxanthone-4-sulfonic acid; benzophenones such as benzophenone,4-benzoyl-4′-methyldiphenylsulfide, 4,4′-bismethylaminobenzophenone,4,4′-bis(dimethylamino)benzophenone, and4,4′-bis(diethylamino)benzophenone; acetophenones such as acetophenone,2-(4-toluenesulfonyloxy)-2-phenylacetophenone,p-dimethylaminoacetophenone, 2,2′-dimethoxy-2-phenylacetophenone,2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone,2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone,1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, p-methoxyacetophenone,2-methyl[4-(methylthio)phenyl]-2-morpholino-1-propanone, and2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; quinonessuch as anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone,2-chloroanthraquinone, 2-amylanthraquinone, and 1,4-naphthoquinone;ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal;aminobenzoic acids such as ethyl 2-dimethylaminobenzoate, ethyl4-dimethylaminobenzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate,isoamyl 4-dimethylaminobenzoate, and 2-ethylhexyl4-dimethylaminobenzoate; halogen compounds such as phenacyl chloride andtrihalomethyl phenyl sulfone; acylphosphine oxides such as2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide,bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, andbis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; peroxides such asdi-t-butyl peroxide; and mixtures thereof. In order to achieve goodlight resistance, i.e., to reduce yellowing of the polymer layer 6,preferred are 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide andbis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

Examples of known radical photo-polymerization initiators include:

“Irgacure® 651” (BASF SE): 2,2-dimethoxy-1,2-diphenylethan-1-one,

“Irgacure 184” (BASF SE): 1-hydroxy-cyclohexyl-phenyl-ketone,

“Irgacure 2959” (BASF SE):1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one,

“Irgacure 127” (BASF SE):2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one,

“Irgacure 907” (BASF SE):2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one,

“Irgacure 369” (BASF SE):2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone,

“Irgacure 379” (BASF SE):2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone,

“Irgacure 819” (BASF SE): bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide,

“Irgacure 784” (BASF SE):bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium,

“Irgacure OXE 01” (BASF SE): 1,2-octanedione, 1-[4-(phenylthio]-,2-(O-benzoyloxime),

“Irgacure OXE 02” (BASF SE): ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime),

“Irgacure 261” (BASF SE),

“Irgacure 369” (BASF SE),

“Irgacure 500” (BASF SE),

“Irgacure TPO” (BASF SE): 2,4,6-trimethylbenzoyl-diphenyl-phosphineoxide,

“DAROCUR® 1173” (BASF SE): 2-hydroxy-2-methyl-1-phenyl-propan-1-one,

“DAROCUR 1116” (BASF SE),

“DAROCUR 2959” (BASF SE),

“DAROCUR 1664” (BASF SE),

“DAROCUR 4043” (BASF SE),

“Irgacure 754” (BASF SE): Mixture of oxy-phenylacetic acid2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester and oxy-phenylacetic acid2-(2-hydroxyethoxy)ethyl ester,

“Irgacure 500” (BASF SE): Mixture of “Irgacure 184” (BASF SE) andbenzophenone (weight ratio 1:1),

“Irgacure 1300” (BASF SE): Mixture of “Irgacure 369” (BASF SE) and“Irgacure 651” (BASF SE) (weight ratio 3:7),

“Irgacure 1800” (BASF SE): Mixture of “CGI403” (BASF SE) and “Irgacure184” (BASF SE) (weight ratio 1:3),

“Irgacure 1870” (BASF SE): Mixture of “CGI403” (BASF SE) and “Irgacure184” (BASF SE) (weight ratio 7:3), and

“Darocur 4265” (BASF SE): Mixture of “Irgacure TPO” (BASF SE) and“Darocur 1173” (BASF SE) (weight ratio 1:1).

The crosslinking catalyst which is a radical photo-polymerizationinitiator may be used in combination with a sensitizer such as diethylthioxanthone or isopropyl thioxanthone and with a polymerizationaccelerator such as “Darocur EDB” (ethyl-4-dimethylaminobenzoate, BASFSE) and “Darocur EHA” (2-ethylhexyl-4-dimethylaminobenzoate, BASF SE)

The amount of the sensitizer when used is preferably 0.1 to 5 parts bymass, more preferably 0.1 to 2 parts by mass, relative to 100 parts bymass of the curable resin or the curable monomer in the resin 3.

The amount of the polymerization accelerator when used is preferably 0.1to 5 parts by mass, more preferably 0.1 to 2 parts by mass, relative to100 parts by mass of the curable resin or the curable monomer in theresin 3.

The acid generators are materials that generate an acid by applicationof heat or light. Examples of the acid generators include thermal acidgenerators and photo-acid generators. Photo-acid generators arepreferred.

Examples of the thermal acid generators include benzoin tosylate,nitrobenzyl tosylate (especially, 4-nitrobenzyl tosylate), and alkylesters of other organic sulfonic acids.

The photo-acid generators are composed of a chromophore that absorbslight and an acid precursor that is to be converted into an acid afterdecomposition. Application of light of a specific wavelength to aphoto-acid generator of such a structure excites the photo-acidgenerator, generating an acid from the acid precursor moiety.

Examples of the photo-acid generators include salts such as diazoniumsalts, phosphonium salts, sulfonium salts, iodonium salts, CF₃SO₃,p-CH₃PhSO₃, and p-NO₂PhSO₃ (wherein Ph is a phenyl group), organohalogencompounds, orthoquinone-diazide sulfonyl chloride, sulfonic acid esters,2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds,2-trihalomethyl-5-aryl-1,3,4-oxadiazole compounds, and2-trihalomethyl-5-hydroxyphenyl-1,3,4-oxadiazole compounds. Theorganohalogen compounds are compounds that generate a hydrohalic acid(e.g., hydrogen chloride).

Examples of known photo-acid generators include the following.

“WPAG-145” (Wako Pure Chemical Industries, Ltd.):bis(cyclohexylsulfonyl)diazomethane

“WPAG-170” (Wako Pure Chemical Industries, Ltd.):bis(t-butylsulfonyl)diazomethane

“WPAG-199” (Wako Pure Chemical Industries, Ltd.):bis(p-toluenesulfonyl)diazomethane

“WPAG-281” (Wako Pure Chemical Industries, Ltd.): triphenylsulfoniumtrifluoromethanesulfonate

“WPAG-336” (Wako Pure Chemical Industries, Ltd.):diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate

“WPAG-367” (Wako Pure Chemical Industries, Ltd.):diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate

“Irgacure PAG103” (BASF SE):(5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile

“Irgacure PAG108” (BASF SE):(5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile

“Irgacure PAG121” (BASF SE):(5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile

“Irgacure PAG203” (BASF SE)

“CGI 725” (BASF SE)

“TFE-triazine” (Sanwa Chemical Co.):2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine

“TME-triazine” (Sanwa Chemical Co.):2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine

“MP-triazine” (Sanwa Chemical Co.):2-(methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine

“Dimethoxytriazine” (Sanwa Chemical Co.):2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(tri-chloromethyl)-s-triazine

The amount of the crosslinking catalyst is preferably 0.1 to 10 parts bymass, more preferably 0.3 to 5 parts by mass, still more preferably 0.5to 2 parts by mass, relative to 100 parts by mass of the curable resinor the curable monomer in the resin 3. The crosslinking catalyst in anamount within this range can lead to sufficient curing of the resin 3.

When an acid generator is used as the crosslinking catalyst, an acidscavenger may be added as appropriate to control diffusion of the acidgenerated from the acid generator.

The acid scavenger may be any one that does not impair the sublimationand the performance of the resin 3, and is preferably a basic compoundsuch as an amine (particularly, an organic amine), a basic ammoniumsalt, or a basic sulfonium salt, more preferably an organic amine.

Examples of the acid scavenger include 1,5-diazabicyclo[4.3.0]-5-nonene,1,8-diazabicyclo[5.4.0]-7-undecene, 1,4-diazabicyclo[2.2.2]octane,4-dimethylaminopyridine, 1-naphthylamine, piperidine,hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines,4,4′-diaminodiphenyl ether, pyridinium p-toluenesulfonate,2,4,6-trimethylpyridinium p-toluenesulfonate, tetramethylammoniump-toluenesulfonate, tetrabutylammonium lactate, triethylamine, andtributylamine. Preferred among these are organic amines such as1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene,1,4-diazabicyclo[2.2.2]octane, 4-dimethylaminopyridine, 1-naphthylamine,piperidine, hexamethylenetetramine, imidazoles, hydroxypyridines,pyridines, 4,4′-diaminodiphenyl ether, triethylamine, and tributylamine.

The amount of the acid scavenger is preferably 20 parts by mass or less,more preferably 0.1 to 10 parts by mass, still more preferably 0.5 to 5parts by mass, relative to 100 parts by mass of the acid generator.

The resin 3 may contain a solvent (particularly, a water-soluble organicsolvent, an organic solvent (especially, an oil-soluble organicsolvent), or water), as appropriate.

Examples of the water-soluble organic solvent include acetone, methylethyl ketone, methyl amyl ketone, ethyl acetate, propylene glycol,propylene glycol monomethyl ether, propylene glycol monomethyl etheracetate (PGMEA), dipropylene glycol, dipropylene glycol monomethylether, dipropylene glycol dimethyl ether, dipropylene glycol monomethylether acetate, dipropylene glycol diacetate, tripropylene glycol,3-methoxybutyl acetate (MBA), 1,3-butylene glycol diacetate,cyclohexanol acetate, dimethyl formamide, dimethyl sulfoxide, methylcellosolve, cellosolve acetate, butyl cellosolve, butyl carbitol,carbitol acetate, ethyl lactate, isopropyl alcohol, methanol, andethanol.

Examples of the organic solvent include alcohols (e.g., methanol,ethanol, n- or i-propanol, n-, sec-, or t-butanol, benzyl alcohol, andoctanol), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutylketone, diisobutyl ketone, dibutyl ketone, and cyclohexanone), esters orether esters (e.g., ethyl acetate, butyl acetate, and ethyl lactate),ethers (e.g., EG monomethyl ether (methyl cellosolve), EG monoethylether (ethyl cellosolve), diethylene glycol monobutyl ether (butylcellosolve), and propylene glycol monomethyl ether), aromatichydrocarbons (e.g., benzene, toluene, and xylene), amides (e.g.,dimethylformamide, dimethylacetamide, and N-methylpyrrolidone),halogenated hydrocarbons (e.g., methylene dichloride and ethylenedichloride), petroleum-based solvents (e.g., petroleum ether andpetroleum naphtha), γ-butyrolactone, ethylene glycol monomethyl acetate,propylene glycol monomethyl acetate, chloroform, HCFC141b, HCHC225,hydrofluoroether, pentane, hexane, heptane, octane, cyclohexane,tetrahydrofuran, 1,4-dioxane, 1,1,2,2-tetrachloroethane,1,1,1-trichloroethane, trichloroethylene, perchloroethylene,tetrachlorodifluoroethane, and trichlorotrifluoroethane.

The resin 3 may contain one or multiple of these solvents. In order toachieve good solubility and safety of the components in the resin 3,propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate arepreferred.

The resin 3, when containing a solvent, preferably has a solvent contentin the resin 3 of 30 to 95 mass %, more preferably 50 to 90 mass %.

The resin 3 may contain a solvent if necessary as mentioned above, butpreferably contains no solvent. In other words, the resin 3 ispreferably a solvent-free resin. The solvent-free resin enablesreduction in the cost relating to the use of a solvent and inenvironmental load (e.g., bad odor in use). Further, this configurationeliminates the need for a device for removing a solvent, enablingreduction in the cost relating to such a device. In contrast, if theresin 3 contains a solvent, the antifouling agent may be mixedexcessively, so that the fluorine atom concentration on the surface (thesurface opposite to the substrate 2) of the polymer layer 6 may be low.Further, such a resin 3 may have high volatility, so that the ease ofapplication thereof may unfortunately be poor.

The resin 3 may further contain a crosslinker.

The crosslinker is a monofunctional compound or preferably amultifunctional compound containing two or more functional groups. Thecrosslinker is preferably one curable by radical polymerizationreaction, and may be one curable by cationic polymerization reaction.The crosslinker curable by radical polymerization reaction contains afunctional group such as an acryloyl group or a vinyl group which is anunsaturated double bond group. The crosslinker curable by cationicpolymerization reaction contains a functional group such as an epoxygroup, a vinyl ether group, or an oxetane group.

Examples of the crosslinker include (a) urethane (meth)acrylates, (b)epoxy (meth)acrylates, (c) polyester (meth)acrylates, (d) polyether(meth)acrylates, (e) silicone (meth)acrylates, (f) (meth)acrylatemonomers, (g) epoxy monomers, (h) vinyl ether monomers, and (i) oxetanemonomers. The crosslinkers (a) to (f) are those curable by radicalpolymerization reaction and the crosslinkers (g) to (i) are thosecurable by cationic polymerization reaction.

The crosslinkers (a) to (e) contain a (meth)acryloyl group added to theresin, and may also be expressed as oligomers, base resins, orprepolymers in many cases.

The urethane (meth)acrylates (a) are those containing a urethane bondand a (meth)acryloyl group in a molecule. Examples of the urethane(meth)acrylates (a) include poly((meth)acryloyloxyalkyl)isocyanuratestypified by tris(2-hydroxyethyl)isocyanurate diacrylate andtris(2-hydroxyethyl)isocyanurate triacrylate. The isocyanurates aretrifunctional isocyanate compounds. One of these isocyanates may form aurethane bond together with an alkyl group (carbon number 1 to 20), afluoroalkyl group (carbon number 1 to 6), or a perfluoropolyether group(molecular weight 1000 to 50000) and a compound containing a hydroxygroup in one molecule.

The epoxy (meth)acrylates (b) are obtained by adding a (meth)acryloylgroup to an epoxy group, typified by those obtained from a startingmaterial such as bisphenol A, bisphenol F, phenol novolac, or analicyclic compound.

The polyester (meth)acrylates (c) may be ester resins containing apolyhydric alcohol and a polybasic acid with a (meth)acrylate addedthereto. Examples of the polyhydric alcohol include ethylene glycol,1,4-butanediol, 1,6-hexanediol, diethylene glycol, trimethylolpropane,dipropylene glycol, polyethylene glycol, polypropylene glycol,pentaerythritol, and dipentaerythritol. Examples of the polybasic acidinclude phthalic acid, adipic acid, maleic acid, trimellitic acid,itaconic acid, succinic acid, terephthalic acid, and alkenylsuccinicacid.

The polyether (meth)acrylates (d) are polyether resins of a diol with a(meth)acrylate added thereto. Examples of the polyether (meth)acrylates(d) include polyethylene glycol di(meth)acrylate, polypropylene glycoldi(meth)acrylate, and polyethylene glycol-polypropylene glycoldi(meth)acrylate.

The silicone (meth)acrylates (e) are those obtained by modifying atleast one end of dimethyl polysiloxane having a molecular weight of 1000to 10000 with a (meth)acryloyl group, and examples thereof includecompounds represented by the following formula (D24), (D25), or (D26).

The (meth)acrylate monomers (f) are monofunctional or multifunctionalalkyl (meth)acrylates or polyether (meth)acrylates having a lowviscosity of 500 mPa·s or lower (25° C.). Examples of the (meth)acrylatemonomers (f) include methyl (meth)acrylate, ethyl (meth)acrylate,n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl(meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate,t-butyl (meth)acrylate, n-pentyl (meth)acrylate, 3-methylbutyl(meth)acrylate, n-hexyl (meth)acrylate, 2-ethyl-n-hexyl (meth)acrylate,n-octyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl(meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate,2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate,4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate,6-hydroxyhexyl (meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate,neopentyl glycol mono(meth)acrylate, 3-chloro-2-hydroxypropyl(meth)acrylate, (1,1-dimethyl-3-oxobutyl) (meth)acrylate,2-acetoacetoxyethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate,2-ethoxyethyl (meth)acrylate, neopentyl glycol mono(meth)acrylate,3-chloro-2-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate,ethylene glycol diacrylate, propylene glycol diacrylate, 1,6-hexanedioldiacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate,trimethylolpropane triacrylate, and pentaerythritol tetraacrylate.

Examples of the epoxy monomers (g) include epoxy monomers, includingglycidyl ethers of phenols such as bisphenol A, bisphenol F, resorcinol,phenol novolac, and cresol novolac; glycidyl ethers of alcohols such asbutanediol, polyethylene glycol, and polypropylene glycol; and glycidylesters of carboxylic acids such as phthalic acid, isophthalic acid, andtetrahydrophthalic acid, oligomers thereof, and alicyclic epoxidesthereof. Preferred among these are monomers or oligomers of bisphenol Aglycidyl ether. Specific examples thereof include “Epikote 828”(molecular weight 380), “Epikote 834” (molecular weight 470), “Epikote1001” (molecular weight 900), “Epikote 1002” (molecular weight 1060),“Epikote 1055” (molecular weight 1350), and “Epikote 1007” (molecularweight 2900) (Mitsubishi Chemical Corp.).

Examples of the vinyl ether monomers (h) include 2-hydroxyethyl vinylether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether,cis-1,1,3-trimethyl-5-vinyloxycyclohexane,trans-1,1,3-trimethyl-5-vinyloxycyclohexane,1-isopropyl-4-methyl-2-vinyloxycyclohexane,2-vinyloxy-7-oxabicyclo[3.2.1]octan-6-one,2-methyl-2-vinyloxyadamantane, 2-ethyl-2-vinyloxyadamantane,1,3-bis(vinyloxy)adamantane, 1-vinyloxyadamantanol,3-vinyloxy-1-adamantanol, 1,3,5-tris(vinyloxy)adamantane,3,5-bis(vinyloxy)-1-adamantanol, 5-vinyloxy-1,3-adamantanediol,1,3,5,7-tetrakis(vinyloxy)adamantane,3,5,7-tris(vinyloxy)-1-adamantanol,5,7-bis(vinyloxy)-1,3-adamantanediol, 7-vinyloxy-1,3,5-adamantanetriol,1,3-dimethyl-5-vinyloxyadamantane,1,3-dimethyl-5,7-bis(vinyloxy)adamantane,3,5-dimethyl-7-vinyloxy-1-adamantanol, 1-carboxy-3-vinyloxyadamantane,1-amino-3-vinyloxyadamantane, 1-nitro-3-vinyloxyadamantane,1-sulfo-3-vinyloxyadamantane, 1-t-butyloxycarbonyl-3-vinyloxyadamantane,4-oxo-1-vinyloxyadamantane,1-vinyloxy-3-(1-methyl-1-vinyloxyethyl)adamantane,1-(vinyloxymethyl)adamantane, 1-(1-methyl-1-vinyloxyethyl)adamantane,1-(1-ethyl-1-vinyloxyethyl)adamantane,1,3-bis(1-methyl-1-vinyloxyethyl)adamantane,1-(1-(norbornan-2-yl)-1-vinyloxyethyl)adamantane,2,5-bis(vinyloxy)norbornane, 2,3-bis(vinyloxy)norbornane,5-methoxycarbonyl-2-vinyloxynorbornane,2-(1-(norbornan-2-yl)-1-vinyloxyethyl)norbornane,2-(vinyloxymethyl)norbornane, 2-(1-methyl-1-vinyloxyethyl)norbornane,2-(1-methyl-1-vinyloxypentyl)norbornane,3-hydroxy-4-vinyloxytetracyclo[4.4.0.12,5.17,10]dodecane,3,4-bis(vinyloxy)tetracyclo[4.4.0.12,5.17,10]dodecane,3-hydroxy-8-vinyloxytetracyclo[4.4.0.12,5.17,10]dodecane,3,8-bis(vinyloxy)tetracyclo[4.4.0.12,5.17,10]dodecane,3-methoxycarbonyl-8-vinyloxytetracyclo[4.4.0.12,5.17,10]dodecane,3-methoxycarbonyl-9-vinyloxytetracyclo[4.4.0.12,5.17,10]dodecane,3-(vinyloxymethyl)tetracyclo[4.4.0.12,5.17,10]dodecane,3-hydroxymethyl-8-vinyloxytetracyclo[4.4.0.12,5.17,10]dodecane,3-hydroxymethyl-9-vinyloxytetracyclo[4.4.0.12,5.17,10]dodecane,8-hydroxy-3-(vinyloxymethyl)tetracyclo[4.4.0.12,5.17,10]dodecane,9-hydroxy-3-(vinyloxymethyl)tetracyclo[4.4.0.12,5.17,10]dodecane,8-vinyloxy-4-oxatricyclo[5.2.1.02,6]decane-3,5-dione,4-vinyloxy-11-oxapentacyclo[6.5.1.13,6.02,7.09,13]pentadecane-10,12-dione,α-vinyloxy-γ,γ-dimethyl-γ-butyrolactone,α,γ,γ-trimethyl-α-vinyloxy-γ-butyrolactone,γ,γ-dimethyl-β-methoxycarbonyl-α-vinyloxy-γ-butyrolactone,8-vinyloxy-4-oxatricyclo[5.2.1.02,6]decan-3-one,9-vinyloxy-4-oxatricyclo[5.2.1.02,6]decan-3-one,8,9-bis(vinyloxy)-4-oxatricyclo[5.2.1.02,6]decan-3-one,4-vinyloxy-2,7-dioxabicyclo[3.3.0]octan-3,6-dione,5-vinyloxy-3-oxatricyclo[4.2.1.04,8]nonan-2-one,5-methyl-5-vinyloxy-3-oxatricyclo[4.2.1.04,8]nonan-2-one,9-methyl-5-vinyloxy-3-oxatricyclo[4.2.1.04,8]nonan-2-one,6-vinyloxy-3-oxatricyclo[4.3.1.14,8]undecan-2-one,6,8-bis(vinyloxy)-3-oxatricyclo[4.3.1.14,8]undecan-2-one,6-hydroxy-8-vinyloxy-3-oxatricyclo[4.3.1.14,8]undecan-2-one,8-hydroxy-6-vinyloxy-3-oxatricyclo[4.3.1.14,8]undecan-2-one, andisopropenyl ethers corresponding thereto.

Examples of the oxetane monomers (i) include1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]ethyl}benzene (e.g., “AroneOxetane® OXT-121”, Toagosei Co., Ltd.) and3-ethyl-3-hydroxymethyloxetane (e.g., “Arone Oxetane OXT-101”, ToagoseiCo., Ltd.).

The resin 3, when containing an acid generator as a crosslinkingcatalyst, may contain an acid crosslinker as a crosslinker.

The acid crosslinker is a compound containing an acidic group and aplurality of (e.g., 2 to 10) crosslinkable reactive groups (e.g., acarboxylic acid, a hydroxy group, an amino group, an isocyanate group, aN-methylol group, an alkyl-etherified N-methylol group, and an epoxygroup) in one molecule or a polyvalent metal salt of acetic acid.Examples of the acid crosslinker include amino resins, epoxy compounds,oxazoline compounds, and aluminum acetate.

Examples of the amino resins include compounds obtained byhydroxymethylating at least some of amino groups in melamine compounds,guanamine compounds, urea compounds, and the like, and compoundsobtained by etherifying at least some of hydroxy groups of thesehydroxymethylated compounds with methanol, ethanol, n-butyl alcohol,2-methyl-1-propanol, or the like. A specific example thereof ishexamethoxymethyl methylol melamine, and known examples thereof includea variety of alkyl-, methylol-, or imino-type amino resins (Nihon CytecIndustries Inc.).

Examples of the epoxy compounds include glycidyl ethers such asbisphenol A epoxy resins, bisphenol F epoxy resins, phenol-novolac epoxyresins, cresol-novolac epoxy resins, trisphenolmethane epoxy resins, andbrominated epoxy resins; alicyclic epoxy resins such as3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate andbis(2,3-epoxycyclopentyl)ether; glycidyl esters such as diglycidylhexahydrophthalate, diglycidyl tetrahydrophthalate, and diglycidylphthalate; glycidylamines such as tetraglycidyl diaminodiphenylmethaneand triglycidyl paraaminophenol; and heterocyclic epoxy resins such astriglycidyl isocyanurate.

Examples of the oxazoline compounds include copolymers of polymerizablemonomers such as 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline,2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, and2-isopropenyl-4-methyl-2-oxazoline.

The resin 3 may contain an acid crosslinker as a thermal crosslinker.The thermal crosslinker is a crosslinker blended for the purpose ofimproving the crosslinkability of a film during post-baking. In order toimprove the crosslinking density of the thermal crosslinker, the thermalcrosslinker may be used in combination with an acid anhydride of an acidsuch as crotonic acid, itaconic acid, itaconic anhydride, maleic acid,maleic anhydride, fumaric acid, phtahalic anhydride, tetrahydrophthalicanhydride, or cinnamic acid.

Combination use of a crosslinker with a multifunctional thiol such as1,4-bis(3-mercaptobutyryloxy)butane or pentaerythritoltetrakis(3-mercaptobutyrate) can increase the curing rate of the resin3. In this case, the amount of the multifunctional thiol is preferably0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, relativeto 100 parts by mass of the crosslinker.

The die 4 may be one produced by the following method. First, silicondioxide (SiO₂) serving as an insulating material and pure aluminum aresuccessively formed into films on an aluminum substrate (roll like).Next, the resulting pure-aluminum layer is repetitively subjected toanodizing and etching. This can provide a cavity (die 4) of the moth-eyestructure. At this time, the uneven structure of the die 4 can bemodified by adjusting the duration of the anodizing and the duration ofthe etching.

The first release agent 5 contains a compound containing aperfluoro(poly)ether group, a hydrolyzable group (e.g., an alkoxygroup), and a Si atom. This enables easy removal of the die 4 from thepolymer layer 6. Further, this treatment can lead to a low surface freeenergy of the die 4, and thus the fluorine atoms in the antifoulingagent of the resin 3 can efficiently be distributed on the surface (thesurface opposite to the substrate 2) of the resin 3 when the substrate 2is pushed to the die 4 in Process (3). This treatment can also preventearly removal of the fluorine atoms from the surface (the surfaceopposite to the substrate 2) of the resin 3 before curing of the resin3. As a result, in the antifouling film 1, the fluorine atoms canefficiently be distributed on the surface (the surface opposite to thesubstrate 2) of the polymer layer 6.

The compound containing a perfluoro(poly)ether group, a hydrolyzablegroup, and a Si atom may specifically be at least one compound(perfluoropolyether compound) selected from the group consisting of thecompounds represented by the following formulas (1a), (1b), (2a), (2b),(3a), and (3b).

First, the compounds (fluorosilane-containing compounds) represented bythe following formulas (1a), (1b), (2a), and (2b) are described below.

In the formulas (1a), (1b), (2a), and (2b), Rf¹ and Rf² are each aC1-C16 (e.g., linear or branched) alkyl group optionally substitutedwith one or more fluorine atoms, preferably a C1-C3 linear or branchedalkyl group optionally substituted with one or more fluorine atoms. Thealkyl group optionally substituted with one or more fluorine atoms ispreferably a fluoroalkyl group in which the terminal carbon atoms areCF₂H— and the other carbon atoms are substituted with a fluorine atom,or a perfluoroalkyl group, more preferably a perfluoroalkyl group,specifically —CF₃, —CF₂CF₃, or —CF₂CF₂CF₃.

In the formulas (1a), (1b), (2a), and (2b), the perfluoropolyether groupis a moiety represented by—(OC₄F₈)_(s)—(OC₃F₆)_(a)—(OC₂F₄)_(b)—(OCF₂)_(c)—. In the formula, a, b,c, and s are each the number of the four repeating units of theperfluoropolyether constituting the main backbone of the polymer; a, b,c, and s are each individually an integer of 0 to 200 (e.g., an integerof 1 to 200); the sum of a, b, c, and s is 1 or greater, preferably 20to 100, more preferably 30 to 50, typically about 40; and the repeatingunits parenthesized with a, b, c, or s are present in any order in theformulas (1a), (1b), (2a), and (2b). The repeating unit —(OC₄F₈)— may beany of —(OCF₂CF₂CF₂CF₂)—, —(OCF(CF₃) CF₂CF₂)—, —(OCF₂CF(CF₃) CF₂)—,—(OCF₂CF₂CF(CF₃))—, —(OC(CF₃)₂CF₂)—, —(OCF₂C(CF₃)₂)—, and—(OCF(CF₃)CF(CF₃))—, and is preferably —(OCF₂CF₂CF₂CF₂)—. The repeatingunit —(OC₃F₆)— may be any of —(OCF₂CF₂CF₂CF₂)—, —(OCF(CF₃)CF₂)—, and—(OCF₂CF(CF₃))—, and is preferably —(OCF₂CF₂CF₂CF₂)—. The repeating unit—(OC₂F₄)— may be any of —(OCF₂CF₂)— and —(OCF(CF₃))—, and is preferably—(OCF₂CF₂)—.

The compound containing a perfluoropolyether group can improve theantifouling properties (e.g., water repellency, oil repellency, ease ofwiping off fingerprints) of the antifouling film 1.

In the formulas (1a), (1b), (2a), and (2b), d and f are each 0 or 1; eand g are each an integer of 0 to 2; h and j are each 1 or 2; and i andk are each an integer of 2 to 20.

In the formulas (1a), (1b), (2a), and (2b), X is a hydrogen atom or ahalogen atom. The halogen atom is preferably an iodine atom, a chlorineatom, or a fluorine atom, still more preferably an iodine atom.

In the formulas (1a), (1b), (2a), and (2b), Y is a hydrogen atom or alower alkyl group. The lower alkyl group is preferably a C1-C20 alkylgroup.

In the formulas (1a), (1b), (2a), and (2b), Z is a fluorine atom or alower fluoroalkyl group. The lower fluoroalkyl group may be a C1-C3fluoroalkyl group, and is preferably a C1-C3 perfluoroalkyl group, morepreferably a trifluoromethyl group or a pentafluoroethyl group, stillmore preferably a trifluoromethyl group.

The formulas (1a), (1b), (2a), and (2b) are preferably, but not limitedto, such that Rf¹ and Rf² are each a C1-C3 perfluoroalkyl group, b=0,c=0, d=1, f=1, and Z is a fluorine atom. Such a structure can improvethe rubbing resistance. More preferably, the repeating unitparenthesized with a, i.e., —(OC₃F₆)—, is —(OCF₂CF₂CF₂CF₂)— and a=40.Such a structure contains a linear perfluoropolyether group, and thuscan lead to a higher rubbing resistance and is easier to synthesize thanbranched one.

In the formulas (1a), (1b), (2a), and (2b), R¹, R², and T are Si-bindinggroups; and n is an integer of 1 to 3.

In the formulas (1a), (1b), (2a), and (2b), R¹ and R² are each a C1-C22alkyl group, a C1-C22 alkoxy group, or a hydroxy group, preferably aC1-C22 alkyl group or a C1-C22 alkoxy group, more preferably a C1-C3alkyl group or a C1-C3 alkoxy group. The hydroxy group may be, but isnot limited to, one generated by hydrolysis of a hydrolyzable group(e.g., a C1-C22 alkoxy group).

In the formulas (1a), (1b), (2a), and (2b), T is a hydroxy group or ahydrolyzable group.

In the formulas (1a), (1b), (2a), and (2b), m and 1 are each an integerof 1 to 10, preferably an integer of 2 to 6.

The compounds represented by the formulas (1a), (1b), (2a), and (2b)each preferably have a number average molecular weight of 5×10² to1×10⁵, more preferably 2000 to 30000, still more preferably 3000 to10000, particularly preferably 3000 to 8000, although not limitedthereto. The compound having a number average molecular weight withinthe above range can lead to high friction durability and makes it easyto perform a treatment on the die 4. Too small a number averagemolecular weight may cause a failure in giving a sufficiently highfriction durability, while too large a number average molecular weightmay limit the technique for treatment on the die 4.

An exemplary method for producing the compounds represented by theformulas (1a), (1b), (2a), and (2b) is described below, but the methodis not limited thereto.

For the compound represented by one of the formulas (1a) and (1b), atleast one compound represented by one of the following formulas (1a-ii)and (1b-ii) is prepared as a material.

In the formulas (1a-ii) and (1b-ii), X′ is a halogen atom, preferably aniodine atom. In the formulas (1a-ii) and (1b-ii), the symbols other thanX′ are defined in the same manner as in the formulas (1a) and (1b).

The compounds represented by the formulas (1a-ii) and (1b-ii) may beobtained by, but not limited to, halogenating (e.g., iodizing) at leastone compound represented by one of the following formulas (1a-i) and(1b-i).

The symbols in the formulas (1a-i) and (1b-i) are defined in the samemanner as those in the formulas (1a) and (1b).

Then, the at least one compound represented by one of the formulas(1a-ii) and (1b-ii) is reacted with a compound represented by thefollowing formula (E3) or (E4). Thereby, at least one compoundrepresented by one of the formulas (1a) and (1b) is obtained.CH₂═CY—(CH₂)_(e)—SiX″_(n)R¹ _(3-n) and T-H  (E3)CH₂═CY—(CH₂)_(e)-SiT_(n)R¹ _(3-n)  (E4)

In the formulas (E3) and (E4), X″ is a halogen atom. In the formulas(E3) and (E4), the symbols other than X″ are defined in the same manneras those in the formulas (1a) and (1b).

For the compound represented by one of the formulas (2a) and (2b), atleast one compound represented by one of the following formulas (2a-i)and (2b-1) is prepared as a material.

The symbols in the formulas (2a-i) and (2b-i) are defined in the samemanner as those in the formulas (2a) and (2b).

Then, the at least one compound represented by the formula (2a-i) or(2b-i) is hydrosilylated with a compound represented by the followingformula (E5) in the presence of a transition metal (preferably platinumor rhodium).HSiX¹ _(n)R² _(3-n)  (E5)

In the formula (E5), X¹ is a halogen atom, preferably a chlorine atom;and the symbols other than X¹ are defined in the same manner as in theformulas (2a) and (2b).

Thereby, at least one compound represented by one of the followingformulas (2a-ii) and (2b-ii) is obtained.

The symbols in the formulas (2a-ii) and (2b-ii) are defined in the samemanner as those in the formulas (2a), (2b), and (E5).

Then, the at least one compound represented by one of the formulas(2a-ii) and (2b-ii) is dehalogenated with a compound represented by thefollowing formula (E6). Thereby, at least one compound represented byone of the formulas (2a) and (2b) is obtained.TH  (E6)

In the formula (E6), T is defined in the same manner as those in theformulas (2a) and (2b), except for the hydroxy group.

Although the compounds represented by the formulas (1a), (1b), (2a), and(2b) are described hereinabove, these compounds are not limited to thoseproduced by the above methods.

Next, the compounds (fluorosilane-containing compounds) represented bythe following formulas (3a) and (3b) are described below.A-Rf—X-SiQ_(k)Y_(3-k)  (3a)Y_(3-k)Q_(k)Si—X—Rf—X-SiQ_(k)Y_(3-k)  (3b)

In the formulas (3a) and (3b), A is a C1-C16 alkyl group optionallysubstituted with one or more fluorine atoms. The “C1-C16 alkyl group” inthe C1-C16 alkyl group optionally substituted with one or more fluorineatoms is a linear or branched C1-C16 alkyl group, preferably a linear orbranched C1-C6, particularly C1-C3, alkyl group, more preferably alinear C1-C3 alkyl group.

In the formulas (3a) and (3b), A is preferably a C1-C16 alkyl groupsubstituted with one or more fluorine atoms, more preferably aCF₂H—C₁₋₁₅ perfluoroalkylene group, still more preferably a C1-C16perfluoroalkyl group.

The C1-C16 perfluoroalkyl group is a linear or branched C1-C16perfluoroalkyl group, preferably a linear or branched C1-C6,particularly C1-C3, perfluoroalkyl group, more preferably a linear C1-C3perfluoroalkyl group (specifically, —CF₃, —CF₂CF₃, or —CF₂CF₂CF₃).

In the formulas (3a) and (3b), Rf is a group represented by thefollowing formula (E1), which corresponds to a perfluoropolyether group.—(OC₄F₈)_(a)—(OC₃F₆)_(b)—(OC₂F₄)_(c)—(OCF₂)_(d)—  (E1)

In the formula (E1), a, b, c, and d are each individually an integer of0 or greater, with the sum of them being 1 or greater; a, b, c, and dare preferably each individually an integer of 0 to 200 (e.g., aninteger of 1 to 200), more preferably each individually an integer of 0to 100 (e.g., an integer of 1 to 100). The sum of a, b, c, and d isstill more preferably 10 or greater (preferably 20 or greater) and 200or smaller (preferably 100 or smaller). The repeating unitsparenthesized with a, b, c, or d are present in any order in the formula(E1). For these repeating units, —(OC₄F₈)— may be any of—(OCF₂CF₂CF₂CF₂)—, —(OCF(CF₃) CF₂CF₂)—, —(OCF₂CF(CF₃) CF₂)—,—(OCF₂CF₂CF(CF₃))—, —(OC(CF₃)₂CF₂)—, —(OCF₂C(CF₃)₂)—, —(OCF(CF₃)CF(CF₃))—, —(OCF(C2F₅)CF₂)—, and —(OCF₂CF(C₂F₅))—, preferably—(OCF₂CF₂CF₂CF₂)—; —(OC₃F₆)— may be any of —(OCF₂CF₂CF₂CF₂)—,—(OCF(CF₃)CF₂)—, and —(OCF₂CF(CF₃))—, preferably —(OCF₂CF₂CF₂CF₂)—; and—(OC₂F₄)— may be either of —(OCF₂CF₂)— and —(OCF(CF₃))—, preferably—(OCF₂CF₂)—.

In an embodiment, Rf in the formulas (3a) and (3b) may be a grouprepresented by the following formula (E7), and is preferably a grouprepresented by the following formula (E8).—(OC₃F₆)_(b)—  (E7)

In the formula (E7), b is an integer of 1 to 200, preferably an integerof 10 to 100.—(OCF₂CF₂CF₂CF₂)_(b)—  (E8)

In the formula (E8), b is defined in the same manner as b in the formula(E7).

In another embodiment, Rf in the formulas (3a) and (3b) may be a grouprepresented by the following formula (E9), and is preferably a grouprepresented by the following formula (E10).—(OC₄F₈)_(a)—(OC₃F₆)_(b)—(OC₂F₄)_(c)—(OCF₂)_(d)—  (E9)

In the formula (E9), a and b are each individually an integer of 0 to30, preferably an integer of 0 to 10; c and d are each individually aninteger of 1 to 200, preferably an integer of 10 to 100; the sum of a,b, c, and d is 10 or greater (preferably 20 or greater) and 200 orsmaller (preferably 100 or smaller); and the repeating unitsparenthesized with a, b, c, or d are present in any order in the formula(E9).—(OCF₂CF₂CF₂CF₂)_(a)—(OCF₂CF₂CF₂CF₂)_(b)—(OCF₂CF₂)_(c)—(OCF₂)_(d)—  (E10)

In the formula (E10), a, b, c, and d are defined in the same manner asa, b, c, and d in the formula (E9).

In the formulas (3a) and (3b), X is a divalent organic group. In thecompounds represented by the formulas (3a) and (3b), X is understood asa linker coupling a perfluoropolyether moiety (A-Rf— moiety or —Rf—moiety) mainly providing water repellency and smoothness and a silanemoiety (—SiQ_(k)Y_(3-k), moiety) that is to be hydrolyzed to provide anability to bind to the die 4. Thus, this X may be any divalent organicgroup that allows the compounds represented by the formulas (3a) and(3b) to be present stably.

X in the formulas (3a) and (3b) may be, but is not limited to, a grouprepresented by the following formula (E11):—(R⁶)_(p)—(X¹)_(q)—R⁷—  (E11)wherein R⁶ is —(CH₂)_(s)— or an o-, m-, or p-phenylene group, preferably—(CH₂)_(s)—; R⁷ is —(CH₂)_(t)— or an o-, m-, or p-phenylene group,preferably —(CH₂)_(t)—; X¹ is —(X²)_(r)—; X²s are each individually —O—,—S—, an o-, m-, or p-phenylene group, —C(O)O—, —CONR⁵—, —O—CONR⁵—,—NR⁵—, —Si(R³)₂—, —(Si(R³)₂O)_(m)—Si(R³)₂—, or —(CH₂)_(v)—; R³s are eachindividually a phenyl group or a C1-C6 alkyl group, preferably a C1-C6alkyl group, more preferably a methyl group; R⁵s are each individually ahydrogen atom, a phenyl group, or a C1-C6 alkyl group (preferably amethyl group); each m is individually an integer of 1 to 100, preferablyan integer of 1 to 20; each v is individually an integer of 1 to 20,preferably an integer of 1 to 6, more preferably an integer of 1 to 3; sis an integer of 1 to 20, preferably an integer of 1 to 6, morepreferably an integer of 1 to 3, still more preferably 1 or 2; t is aninteger of 1 to 20, preferably an integer of 2 to 6, more preferably aninteger of 2 or 3; r is an integer of 1 to 10, preferably an integer of1 to 5, more preferably an integer of 1 to 3; p is 0 or 1; and q is 0 or1.

In the formulas (3a) and (3b), X is preferably a C1-C20 alkylene group,a group represented by the following formula (E12), or a grouprepresented by the following formula (E13), more preferably a C1-C20alkylene group, a group represented by the following formula (E14), or agroup represented by the following formula (E15).—R⁶—X³—R⁷—  (E12)—X⁴—R⁷—  (E13)

In the formulas (E12) and (E13), R⁶ and R⁷ are defined in the samemanner as R⁶ and R⁷ in the formula (E11).—(CH₂)_(s)—X³—(CH₂)_(t)—  (E14)—X⁴—(CH₂)_(t)—  (E15)

In the formulas (E14) and (E15), s and t are defined in the same manneras s and t in the formula (E11).

In the formulas (E12) and (E14), X³ is —O—, —S—, —C(O)O—, —CONR⁵—,—O—CONR⁵—, —Si(R³)₂—, —(Si(R³)₂O)_(m)—Si(R³)₂—, —O—(CH₂)_(u)—(Si(R³)₂O)m-Si(R³)₂—, —CONR⁵—(CH₂)_(u)—(Si(R³)₂O)_(m)—Si(R³)₂—,—CONR⁵—(CH₂)_(v)—N(R⁵)—, or —CONR⁵— (o-, m-, or p-phenylene)-Si(R³)₂—,wherein R³, R⁵, m, and v are defined in the same manner as R³, R⁵, m,and v in the formula (E11); and u is an integer of 1 to 20, preferablyan integer of 2 to 6, more preferably an integer of 2 or 3. X³ ispreferably —O—.

In the formulas (E13) and (E15), X⁴ is —S—, —C(O)O—, —CONR⁵—,—CONR⁵—(CH₂)_(u)—(Si(R³)₂O)_(m)—Si(R³)₂—, —CONR⁵—(CH₂)_(v)—N(R⁵)—, or—CONR⁵— (o-, m-, or p-phenylene)-Si(R³)₂—, wherein R³, R⁵, m, and v aredefined in the same manner as R³, R⁵, m, and v in the formula (E11); andu is an integer of 1 to 20, preferably an integer of 2 to 6, morepreferably an integer of 2 or 3.

In the formulas (3a) and (3b), X is still more preferably a C1-C20alkylene group, a group represented by the following formula (E16), agroup represented by the following formula (E17), or a group representedby the following formula (E18).—(CH₂)_(s)—O—(CH₂)_(t)—  (E16)—(CH₂)_(s)—(Si(R³)₂O)_(m)—Si(R³)₂—(CH₂)_(t)—  (E17)—(CH₂)_(s)—O—(CH₂)_(u)—(Si(R³)₂O)_(m)—Si(R³)₂—(CH₂)_(t)—  (E18)

The symbols in the formulas (E16), (E17), and (E18) are defined in thesame manner as the symbols in the formulas (E12), (E13), (E14), and(E15).

In the formulas (3a) and (3b), X may be substituted with at least onesubstituent selected from the group consisting of a fluorine atom, aC1-C3 alkyl group, and a C1-C3 fluoroalkyl group (preferably, a C1-C3perfluoroalkyl group).

In the formulas (3a) and (3b), Y is a hydroxy group, a hydrolyzablegroup, or a hydrocarbon group. The hydroxy group may be, but is notlimited to, one generated by hydrolysis of a hydrolyzable group (e.g., aC1-C22 alkoxy group).

In the formulas (3a) and (3b), Y is preferably a hydroxy group, a C1-C12alkyl group, a C2-C12 alkenyl group, a C2-C12 alkynyl group, a phenylgroup, or a group represented by the following formula (E19), morepreferably —OCH₃, —OCH₂CH₃, or —OCH(CH₃)₂. These groups may besubstituted with at least one substituent selected from the groupconsisting of a fluorine atom, a C1-C6 alkyl group, a C2-C6 alkenylgroup, and a C2-C6 alkynyl group.—O(R⁵)  (E19)

In the formula (E19), R⁵ is a C1-C12 alkyl group, preferably a C1-C6alkyl group, more preferably a C1-C3 alkyl group.

In the formulas (3a) and (3b), Q is a group represented by the followingformula (E2).—Z—SiR¹ _(n)R² _(3-n)  (E2)

In the formula (E2), Zs are each individually a divalent organic group.

In the formula (E2), Z preferably contains no moiety that is to form asiloxane bond with a Si atom at an end of the molecular main chain inthe formula (3a) or (3b).

In the formula (E2), Z is preferably a C1-C6 alkylene group, a grouprepresented by the following formula (E20), or a group represented bythe following formula (E21), more preferably a C1-C3 alkylene group.These groups may be substituted with at least one substituent selectedfrom the group consisting of a fluorine atom, a C1-C6 alkyl group, aC2-C6 alkenyl group, and a C2-C6 alkynyl group.—(CH₂)_(s′)—O—(CH₂)_(t′)—  (E20)

In the formula (E20), s′ is an integer of 1 to 6; and t′ is an integerof 1 to 6.-phenylene-(CH₂)_(u′)—  (E21)

In the formula (E21), u′ is an integer of 0 to 6.

In the formula (E2), R¹s are each individually a hydroxy group or ahydrolyzable group.

In the formula (E2), R¹ is preferably a group represented by thefollowing formula (E22).—OR⁶  (E22)

In the formula (E22), R⁶ is a substituted or non-substituted C1-C3 alkylgroup, preferably a methyl group.

In the formula (E2), R²s are each individually a C1-C22 alkyl group orQ′. Q′ is defined in the same manner as Q in the formulas (3a) and (3b).

In the formula (E2), each n is individually an integer of 0 to 3 and thesum of them is 1 or greater for each of Q and Q′. When n is 0 in Q orQ′, Si in Q or Q′ contains neither a hydroxy group nor a hydrolyzablegroup. Thus, the sum of ns must be 1 or greater.

In the formula (E2), n is preferably 2, more preferably 3, in Q′ at anend of the -Q-Q′₀₋₅ chain that binds to a Si atom at an end of themolecular main chain of the perfluoropolyether group.

When at least one R² is Q′, there are two or more Si atoms linearlylinked via Z in Q represented by the formula (E2). The number of Siatoms linearly linked via Z in Q is at most five. The “number of Siatoms linearly linked via Z in Q” is equivalent to the number ofrepeated —Z—Si-units linearly linked.

An example of the linking structure of Si atoms via Z in Q is shown inthe following formula (E23).

In the formula (E23), the symbol “*” represents the site binding to Siin the main chain. The symbol “---” represents binding of apredetermined group other than ZSi. In other words, when all of thethree bindings of a Si atom are represented by the symbol “---”, itmeans the site where repeat of ZSi is finished. The superscriptimmediately after Si is the number of Si atoms linearly linked from thesymbol “*” via Z. In other words, when the ZSi repeating is finished atSit, the chain is considered as including two “Si atoms linearly linkedvia Z in Q”. Similarly, when ZSi repeating is finished at Si³, Si⁴, andSi⁵, the chain includes three, four, and five “Si atoms linearly linkedvia Z in Q”, respectively. As is clear from the above formula (E23), aplurality of ZSi chains is present in Q. Still, they need not to havethe same length, and may have the respective lengths.

As shown in the following formulas (E24) and (E25), the “number of Siatoms linearly linked via Z in Q” is preferably one (formula (E24)) ortwo (formula (E25)) in all the chains.

In an embodiment, “the number of Si atoms linearly linked via Z in Q”may be one (in other words, only one Si atom is present in Q) or two,and is preferably one.

In the formulas (3a) and (3b), k is an integer of 1 to 3, preferably aninteger of 2 or 3, more preferably 3. When k is 3, the first releaseagent can firmly bind to the die 4, achieving high friction durability.

In an embodiment, in the compounds represented by the formulas (3a) and(3b), R² in Q represented by the formula (E2) may be a C1-C22 alkylgroup.

In another embodiment, in the compounds represented by the formulas (3a)and (3b), at least one R² in Q represented by the formula (E2) may beQ′.

In the compounds represented by the formulas (3a) and (3b), the “A-Rf—”moiety preferably has a number average molecular weight of 500 to 30000,more preferably 1500 to 10000, still more preferably 3000 to 8000,although not limited thereto.

In order to achieve high friction durability, the number averagemolecular weight of the compounds represented by the formulas (3a) and(3b) is preferably, but not limited to, 5×10² to 1×10⁵, more preferably1500 to 30000, still more preferably 2500 to 10000, particularlypreferably 3000 to 8000.

An exemplary method for producing the compounds represented by theformulas (3a) and (3b) is described below, but the method is not limitedthereto.

For the compound represented by the formula (3a) or (3b), a compoundrepresented by the following formula (3a-1) or (3b-1) is prepared.A-Rf—X′—CH═CH₂  (3a-1)CH₂═CH—X′—Rf—X′—CH═CH₂  (3b-1)

In the formulas (3a-1) and (3b-1), A and Rf are defined in the samemanner as A and Rf in the formulas (3a) and (3b); and X¹ is a divalentorganic group.

Then, the compound represented by the formula (3a-1) or (3b-1) isreacted with a compound represented by the following formula (E26):HSiM₃  (E26)wherein Ms are each individually a halogen atom or a C1-C6 alkoxy group.

Thereby, a compound represented by the following formula (3a-2) or(3b-2) is obtained.A-Rf—X′—CH₂—CH₂—SiM₃  (3a-2)M₃Si—CH₂—CH₂—X′—Rf—X′—CH₂—CH₂—SiM₃  (3b-2)

In the formulas (3a-2) and (3b-2), A and Rf are defined in the samemanner as A and Rf in the formulas (3a) and (3b); X′ is defined in thesame manner as X′ in the formulas (3a-1) and (3b-1); and M is defined inthe same manner as M in the formula (E26).

Then, the compound represented by the formula (3a-2) or (3b-2) isreacted with a compound represented by the following formula (E27) and,if necessary, a compound represented by the following formula (E28).Hal-J-Z′—CH═CH₂  (E27)

In the formula (E27), Z′ is a bond or a divalent linker group; J is Mg,Cu, Pd, or Zn; and Hal is a halogen atom.Y_(h)L  (E28)

In the formula (E28), Y is defined in the same manner as Y in theformulas (3a) and (3b); L is a group capable of binding to Y; and h isan integer of 1 to 3.

Thereby, a compound represented by the following formula (3a-3) or(3b-3) is obtained.A-Rf—X′—CH₂—CH₂—Si(Y_(3-k′))(—Z′—CH═CH₂)_(k′)  (3a-3)(CH₂═CH—Z′—)_(k′)(Y_(3-k′))Si—CH₂—CH₂—X′—Rf—**X′—CH₂—CH₂—Si(Y_(3k′))(—Z′—CH═CH₂)_(k′)  (3b-3)

In the formulas (3a-3) and (3b-3), A, Rf, and Y are defined in the samemanner as A, Rf, and Y in the formulas (3a) and (3b); X′ is defined inthe same manner as X′ in the formulas (3a-1) and (3b-1); Z′ is definedin the same manner as Z′ in the formula (E27); and k′ is an integer of 1to 3.

Then, the compound represented by the formula (3a-3) or (3b-3) isreacted with the compound represented by the formula (E26) and, ifnecessary, at least one selected from a compound represented by thefollowing formula (E29) and a compound represented by the followingformula (E30). Thereby, a compound represented by the formula (3a) or(3b) is obtained.R¹ _(i)L′  (E29)

In the formula (E29), R¹ is defined in the same manner as R¹ in theformula (E2); L′ is a group capable of binding to R¹; and i is aninteger of 1 to 3.R^(2′) _(j)L″  (E30)

In the formula (E30), R^(2′) is a C1-C22 alkyl group; L″ is a groupcapable of binding to R^(2′); and j is an integer of 1 to 3.

Known examples of at least one compound (perfluoropolyether compound)selected from the group consisting of the compounds represented by theformulas (1a), (1b), (2a), (2b), (3a), and (3b) include “Optool DSX”,“Optool DSX-E”, and “Optool UD100” (Daikin Industries, Ltd.) and“KY-164” and “KY-108” (Shin-Etsu Chemical Co., Ltd.).

The first release agent 5 may contain a perfluoroalkyl compound inaddition to at least one compound (perfluoropolyether compound) selectedfrom the group consisting of the compounds represented by the formulas(1a), (1b), (2a), (2b), (3a), and (3b).

Examples of the perfluoroalkyl compound include C₈F₁₇CH₂CH₂Si(OMe)₃,C6F₁₃CH₂CH₂Si(OMe)₃, and C₄F₉CH₂CH₂Si(OMe)₃.

The second release agent 8 contains a compound (perfluoropolyethercompound) represented by the following formula (F):R¹¹¹—(R¹¹²O)_(m)—R¹¹³  (F)wherein R¹¹¹ and R¹¹³ are each individually a fluorine atom or a —OHgroup; R¹¹² is a C1-C4 fluorinated alkylene group; and m is an integerof 2 or greater.

In the formula (F), m is preferably an integer of 2 to 300, morepreferably an integer of 2 to 100.

In the formula (F), R¹¹² is preferably a C1-C4 perfluorinated alkylenegroup. Examples of —R¹¹²O— in the formula (F) include:

compounds represented by the following formula:—(CX¹¹²₂CF₂CF₂O)_(n111)(CF(CF₃)CF₂O)_(n112)(CF₂CF₂O)_(n113)(CF₂O)_(n114)(C₄F₈O)_(n115)—  (F1)wherein n111, n112, n113, n114, and n115 are each individually aninteger of 0 or 1 or greater; X¹¹² is a hydrogen atom, a fluorine atom,or a chlorine atom; and the repeating units parenthesized with n111,n112, n113, n114, or n115 are present in any order in the formula (F1);and

compounds represented by the following formula:—(OC₂F₄—R¹¹⁸)_(f)—  (F2)wherein R¹¹⁸ is at least one group selected from the group consisting ofOC₂F₄, OC₃F₆, and OC₄F₈; and f is an integer of 2 to 100.

In the formula (F1), n111 to n115 are each preferably an integer of 0 to200. The sum of n111 to n115 is preferably 1 or greater, more preferably5 to 300, still more preferably 10 to 200, particularly preferably 10 to100.

In the formula (F2), R¹¹⁸ is a group selected from OC₂F₄, OC₃F₆, andOC₄F₈, or any combination of two or three groups individually selectedfrom these groups. Examples of the combination of two or three groupsindividually selected from OC₂F₄, OC₃F₆, and OC₄F₈ include, but are notlimited to, —OC₂F₄OC₃F₆—, —OC₂F₄OC₄F₈—, —OC₃F₆OC₂F₄—, —OC₃F₆OC₃F₆—,—OC₃F₆OC₄F₈—, —OC₄F₈OC₄F₈—, —OC₄F₈OC₃F₆—, —OC₄F₈OC₂F₄—,—OC₂F₄OC₂F₄OC₃F₆—, —OC₂F₄OC₂F₄OC₄F₈—, —OC₂F₄OC₃F₆OC₂F₄—,—OC₂F₄OC₃F₆OC₃F₆—, —OC₂F₄OC₄F₈OC₂F₄—, —OC₃F₆OC₂F₄OC₂F₄—,—OC₃F₆OC₂F₄OC₃F₆—, —OC₃F₆OC₃F₆OC₂F₄—, and —OC₄F₈OC₂F₄OC₂F₄—. In theformula (F₂), f is preferably an integer of 2 to 50. In the formula(F₂), OC₂F₄, OC₃F₆, and OC₄F₈ each may be linear or branched, and ispreferably linear. In this case, the formula (F₂) is preferably thefollowing formula (F₃) or (F₄).—(OC₂F₄—OC₃F₆)_(f)—  (F₃)—(OC₂F₄—OC₄F₈)_(f)—  (F₄)

The compound represented by the formula (F) preferably has a weightaverage molecular weight of 500 to 100000, more preferably 500 to 50000,still more preferably 500 to 10000, particularly preferably 500 to 6000.The weight average molecular weight can be determined by gel permeationchromatography (GPC).

Examples of known compounds represented by the formula (F) include“Demnum®” (Daikin Industries, Ltd.), “Fomblin®” (Solvay SpecialtyPolymers Japan K. K.), “Barrierta®” (NOK Kluber Co., Ltd.), and“Krytox®” (DuPont).

The second release agent 8 may contain only the compound represented bythe formula (F). Still, in order to achieve low surface energy and easyapplication, the second release agent 8 preferably contains a solvent(other than the compound represented by the formula (F)), morepreferably a fluorosolvent (other than the compound represented by theformula (F)), in addition to the compound represented by the formula(F).

Examples of the fluorosolvent include perfluorohexane,perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane,dichloropentafluoropropane, hydrofluoroether (HFE),hexafluorometaxylene, and Zeorora H (Zeon Corp.). Preferred ishydrofluoroether. The hydrofluoroether is preferably a compoundrepresented by the following formula (F₅), such as C₃F₇OCH₃, C₄F₉OCH₃,C₄F₉OC₂H₅, or C₂F₅CF(OCH₃) C₃F₇.Rf²¹—O—R²¹  (F5)

In the formula (F₅), Rf²¹ is a C₁-C₁₀ fluorinated alkyl group; and R²¹is a C₁-C₃ non-fluorinated alkyl group.

The second release agent 8 which contains a solvent preferably contains0.001 to 10 mass %, more preferably 0.01 to 1 mass %, of the compoundrepresented by the formula (F) relative to the whole amount of thesecond release agent 8. The compound represented by the formula (F) inan amount within the above range allows the second release agent 8 to beapplied easily.

The thickness Q of the polymer layer 6 is preferably 1 μm or greater and20 μm or smaller, more preferably 3 μm or greater and 10 μm or smaller.If the die 4 has local deformation or foreign substances other than thedesired uneven structure, the polymer layer 6 having a thickness Q ofsmaller than 1 μm may cause easy sighting of defects (e.g., deformationtransferred from the die 4, foreign substances) of the antifouling film1. The polymer layer 6 having a thickness Q of greater than 20 μm maycause defects such as curling of the antifouling film 1 due to curingand shrinkage of the resin 3. As shown in FIG. 1-2(e), the thickness Qof the polymer layer 6 means the distance from the surface close to thesubstrate 2 to the apex of a projection 7.

Examples of the shape of the projections 7 include those tapering towardthe tip (a tapered shape) such as shapes consisting of a columnar lowerpart and a hemispherical upper part (temple-bell-like shapes) andconical shapes (cone-like shapes, circular-cone-like shapes). In FIG.1-2(e), the bases of the gaps between any adjacent projections 7 areinclined, but the bases may not be inclined but may be flat.

The pitch P between adjacent projections 7 may be any value that is notlonger than the wavelength of visible light (780 nm), and is preferably20 nm or greater and 400 nm or smaller, more preferably 50 nm or greaterand 300 nm or smaller. Adjacent projections 7 with a pitch P of smallerthan 20 nm may have insufficient mechanical strength, causing poorrubbing resistance of the antifouling film 1. Adjacent projections 7with a pitch P of greater than 400 nm may cause occurrence ofundesirable appearance of the antifouling film 1 due to unnecessaryphenomena such as diffraction and scattering caused by the unevenstructure. The pitch between adjacent projections as used herein can bedetermined as an average value of distances of any adjacent projections(distances between the apexes thereof) in a 2D picture taken with ascanning electron microscope. For example, a 2D picture (magnification:20000×) of the uneven structure is first taken using a scanning electronmicroscope. For about 200 projections within an area of several squaremicrometers of the picture, a combination of three projections isselected which shows the shortest distance between the adjacentprojections. Then, the distances between any two of the threeprojections are measured and the average value thereof is calculated.Thereby, the pitch between adjacent projections (average distancebetween adjacent projections) is determined.

Each projection 7 preferably has a height of 50 nm or greater and 500 nmor smaller, more preferably 100 nm or greater and 400 nm or smaller.Projections 7 having a height of smaller than 50 nm may causeinsufficient antireflective performance of the antifouling film 1.

Projections 7 having a height of greater than 500 nm may haveinsufficient mechanical strength, causing poor rubbing resistance of theantifouling film 1.

Each projection 7 preferably has an aspect ratio of 0.13 or greater and25 or smaller, more preferably 0.3 or greater and 8 or smaller. Theaspect ratio of a projection as used herein means the ratio of theheight of the projection of interest and the pitch between adjacentprojections (height/pitch). A preferred aspect ratio of the projection 7is determined by a preferred range of the pitch P between adjacentprojections 7 and a preferred range of the height of the projection 7 inconsideration of the mechanical strength (rubbing resistance) and theoptical performance (antireflective performance and performance ofpreventing unnecessary phenomena such as diffraction and scattering).

The projections 7 may be arranged either randomly or regularly(periodically). The projections 7 may be arranged with periodicity.Still, in order to successfully avoid unnecessary diffraction of lightdue to such periodicity, the projections 7 are preferably arrangedwithout periodicity (arranged randomly).

Consequently, in the method for producing an antifouling film of theembodiment, the second release agent 8 having low reactivity with thefirst release agent 5 is applied to the surface of the die 4 coated withthe first release agent 5, and thus the method can preventphysicochemical contact between the resin 3 and the first release agent5. This makes it possible to maintain the releasability of the die 4even after long-term continuous formation of the uneven structure withthe die 4. Further, the resin 3 used contains an antifouling agent thatcontains a compound containing a perfluoro(poly)ether group and thefirst release agent 5 used contains a compound that contains aperfluoro(poly)ether group, a hydrolyzable group, and a Si atom. Thiscan lead to high affinity therebetween. As a result, the antifoulingagent in the resin 3 can be efficiently bled out, enabling production ofthe antifouling film 1 having excellent antifouling properties. In otherwords, the method for producing an antifouling film of the embodimentenables long-term continuous production of the antifouling film 1 havingexcellent antifouling properties.

Hereinafter, the present invention is described in more detail based onexamples and comparative examples. The examples, however, are notintended to limit the scope of the present invention.

[Evaluation 1: evaluation based on the presence of second release agent]

For the presence of the second release agent, the antifouling film wasevaluated.

The materials used for producing the antifouling films were as follows.

(Substrate 2)

“Fujitac® TD-60” from Fujifilm Corp. was used. The thickness thereof was60 μm.

(Resin 3)

A resin A1 prepared by mixing the following materials was used. Thenumerical values attached to the materials represent the proportions ofthe materials in the resin A1.

<Antifouling Agent>

-   -   “Antifouling agent A”: 12.5 wt %

The antifouling agent A was produced by the following method, andcontained a perfluoropolyether compound. First, in a reactor, 57 g of“Sumidur N3300” (Sumika Bayer Urethane Co., Ltd., cyclic trimer ofhexamethylene diisocyanate, NCO content: 21.9%) was dissolved in 1000 gof “Zeorora® H” (Zeon Corp.), and 0.1 g of dibutyltin dilaurate (1stGrade, Wako Pure Chemical Industries, Ltd.) was added thereto. To themixture was dropwise added a solution of 244 g of“CF₃CF₂O—(CF₂CF₂CF₂O)₁₁—CF₂CF₂CH₂OH” dissolved in 300 g of “Zeorora H”(Zeon Corp.) under stirring at room temperature. This mixture wascontinuously stirred at room temperature overnight. The mixture was thenwarmed, and 24.4 g of hydroxyethyl acrylate was dropwise added theretoand the mixture was stirred. The reaction end point was defined as thepoint at which the NCO absorption completely disappeared in IR. Next,650 g of 4-acryloylmorpholine was added to the resulting reactionproduct. While the mixture was warmed under reduced pressure, “ZeororaH” (Zeon Corp.) was distilled off. Then, ¹⁹F-NMR was performed toconfirm that the peak of “Zeorora H” (Zeon Corp.) was below thedetection limit. Thereby, the antifouling agent A was obtained. Theantifouling agent A contained 40 wt % of the active component. In otherwords, the amount of the active component of the antifouling agent A inthe resin A1 was 5 wt %.

<Monomer>

-   -   “UA-510H” (Kyoeisha Chemical Co., Ltd.): 8 wt %    -   “ATM-35E” (Shin Nakamura Chemical Co., Ltd.): 41 wt %    -   “Light Acrylate DPE-6A” (Kyoeisha Chemical Co., Ltd.): 19 wt %    -   “DMAA” (KJ Chemicals Corp.): 17.5 wt %        <Polymerization Initiator>    -   “Irgacure 819” (BASF SE): 2 wt %        (Die 4)

A die produced by the following method was used. First, a film ofaluminum that is a material of the die 4 was formed on a surface of a10-cm-square glass substrate by sputtering. The thickness of theresulting aluminum layer was 1.0 μm. Next, the resulting aluminum layerwas repetitively subjected to anodizing and etching (immediately afterthe anodizing). Thereby, an anodizing layer was formed with many finepores (distance between the bottom points of adjacent pores (recesses)was not longer than the wavelength of visible light). Specifically,anodizing, etching, anodizing, etching, anodizing, etching, anodizing,etching, and anodizing were performed successively (anodizing: 5 times,etching: 4 times), so that a die 4 having an uneven structure wasobtained. Fine pores (recesses) formed by such alternate repeating ofanodizing and etching each taper toward the inside of the aluminum layer(having a tapered shape). The anodizing was performed using oxalic acid(concentration: 0.6 wt %) at a liquid temperature of 5° C. and anapplied voltage of 80 V. The duration of a single anodizing process was20 seconds. The etching was performed using phosphoric acid(concentration: 1 mol/l) at a liquid temperature of 30° C. The durationof a single etching process was 25 minutes. The die 4 was found to havea pitch between adjacent recesses (distance between the bottom points)of about 180 nm and a recess depth of about 180 nm by scanning electronmicroscopic observation. Each recess had a conical shape.

(First Release Agent 5)

-   -   “First release agent A”: “Optool DSX” (Daikin Industries, Ltd.)        (Second Release Agent 8)

The following two agents were used as the second release agents 8.

(1) “Second Release Agent A”

The second release agent A contained 0.05 wt % of a compound(perfluoropolyether compound) represented by the following formula (T1)as a solid component and 99.95 wt % of “Novec® 7300” (3M Co.) as afluorosolvent.CF₃CF₂O—(CF₂CF₂CF₂O)₁₁—CF₂CF₂CH₂OH  (T1)(2) “Second Release Agent B”

The second release agent B contained 0.01 wt % of a compound(perfluoropolyether compound) represented by the following formula (T2)as a solid component and 99.99 wt % of “Novec 7300” (3M Co.) as afluorosolvent.CF₃CF₂O—(CF₂CF₂CF₂O)₁₁—CF₂CF₃  (T2)

Example 1

An antifouling film of Example 1 was produced by the method forproducing an antifouling film of the embodiment.

(a) Application of Resin (Process (1))

The resin 3 was applied to a surface of the substrate 2 using a barcoater “No. 02” (Dai-ichi Rika). The resin 3 used was the aforementionedresin A1, and the thickness thereof was 7 μm.

Separately, the die 4 was prepared. A surface of the die 4 was coatedwith the first release agent 5 and had undergone release treatment.Specifically, first, a dilution of the first release agent 5 in “S-135”(Fluoro Technology Co., Ltd.) was prepared. The concentration of thefirst release agent 5 in the dilution was 0.1%. Next, the surface of thedie 4 was subjected to O₂ asking at 200 W for 20 minutes. Then, the die4 was immersed in the dilution of the first release agent 5 for threeminutes, so that the surface of the die 4 was coated with the firstrelease agent 5. The die 4 with the surface coated with the firstrelease agent 5 was annealed at 100° C. for one hour, and then rinsedwith “S-135” (Fluoro Technology Co., Ltd.) for three minutes.

(b) Application of Second Release Agent (Process (2))

The second release agent 8 was applied (potted) to the surface of thedie 4 coated with the first release agent 5. The surface of the die 4coated with the second release agent 8 was covered with a polyethyleneterephthalate film, and the second release agent 8 was spread with ahand roller with the polyethylene terephthalate film in between.Thereby, the second release agent 8 was placed on the first releaseagent 5 on the side opposite to the die 4.

(c) Formation of Uneven Structure (Process (3))

The polyethylene terephthalate film on the surface of the die 4 wasremoved. Then, the substrate 2 was pushed to the surface of the die 4coated with the second release agent 8 with the resin 3 in between andthe resin 3 was spread with a hand roller. Thereby, the uneven structurewas formed on the surface (the surface opposite to the substrate 2) ofthe resin 3.

(d) Curing of resin (Process (4))

The resin 3 having the uneven structure on the surface thereof wasirradiated with and cured by ultraviolet rays (dose: 1 J/cm²) from thesubstrate 2 side using a UV lamp “Light Hanmar 6J6P3” (Heraeus Holding),so that the polymer layer 6 was formed. The thickness Q of the polymerlayer 6 was 7 μm.

(e) Release of Die

The die 4 was released from the polymer layer 6. Thereby, theantifouling film 1 was completed.

The above processes (a) to (e) were repeated 20 times. In the following,the antifouling film obtained by repeating the processes N times isreferred to as an “antifouling film (N times)”. The die after theprocesses are repeated N times is referred to as a “die (N times)”.

Example 2

An antifouling film of Example 2 was produced in the same manner as inExample 1, except that the composition was changed as shown in Table 1.

Comparative Example 1

An antifouling film of Comparative Example 1 was produced in the samemanner as in Example 1, except that the process (b) was not performed(the second release agent was not used).

(Evaluation Contents and Evaluation Results)

The antifouling films and the dies in Examples 1 and 2 and ComparativeExample 1 were evaluated.

(1) Antifouling Film

For the antifouling film (1 time) and the antifouling film (20 times),the antifouling properties and the reflectivity were evaluated.

<Antifouling Properties>

For the antifouling properties, the water repellency and the ease ofwiping off were evaluated. The results are shown in Table 1.

The water repellency was evaluated by the contact angle of water on thesurface (the surface opposite to the substrate of the polymer layer) ofthe antifouling film of each example. Specifically, water was dropped onthe surface (the surface opposite to the substrate of the polymer layer)of the antifouling film of each example, and the contact angle thereofwas measured immediately after the dropping.

The contact angle was the average value of contact angles measured atthe following three points by the θ/2 method (θ/2=arctan(h/r), whereinθ: contact angle, r: radius of droplet, h: height of droplet) using aportable contact angle meter “PCA-1” (Kyowa Interface Science Co.,Ltd.). The first measurement point selected was the central portion ofthe antifouling film of each example. The second and third measurementpoints were two points that are 20 mm or more apart from the firstmeasurement point and are point-symmetrical to each other about thefirst measurement point.

The ease of wiping off was evaluated by whether or not fouling left onthe surface of the antifouling film of each example was wiped off.Specifically, first, “Nivea Creame®” (Nivea-Kao, Co., Ltd.) in imitationof fouling was attached to the surface (the surface opposite to thesubstrate of the polymer layer) of the antifouling film of each example,and was left in an environment at a temperature of 25° C. and a humidityof 40% to 60% for three days. Then, the surface (the surface opposite tothe substrate of the polymer layer) of the antifouling film of eachexample was wiped in one direction 50 times using “Savina®” (KB Seiren,Ltd.). Whether the fouling was wiped off or not was visually observed inan environment with an illuminance of 100 lx. The evaluation criteriawere as follows.

Good: The fouling was wiped off.

Fair: Most part of the fouling was not wiped off.

Poor: The fouling was not wiped off at all.

The cases evaluated as good were considered as within the allowablelevel (having excellent ease of wiping off).

<Reflectivity>

The surface (the surface opposite to the substrate of the polymer layer)of the antifouling film of each example was irradiated with light from alight source at a polar angle of 5°. The regular reflectance at anincident angle of 5° was determined. The measurement of the reflectancewas performed using a spectrophotometer “V-560” (JASCO Corp.) within awavelength range of 250 to 850 nm. In the reflectance measurement, ablack acrylic plate “Acrylite® EX-502” (Mitsubishi Chemical Corp.) wasattached to the back surface (the surface opposite to the polymer layerof the substrate) of the antifouling film of each example, and the lightsource used was a light source C. The measurement results are shown inFIGS. 2 to 4. FIG. 2 is a graph showing the results of measuring thereflectances of an antifouling film (1 time) and an antifouling film (20times) of Example 1. FIG. 3 is a graph showing the results of measuringthe reflectances of an antifouling film (1 time) and an antifouling film(20 times) of Example 2. FIG. 4 is a graph showing the results ofmeasuring the reflectances of an antifouling film (1 time) and anantifouling film (20 times) of Comparative Example 1.

(2) Die

For the die (1 time) and the die (20 times), the releasability wasevaluated.

<Releasability>

For the releasability, the water repellency was evaluated. The resultsare shown in Table 1.

For the water repellency, the contact angle of water on the surface ofthe die of each example was evaluated in the same manner as in the abovemethod. The evaluation was such that a higher contact angle of waterindicated a higher releasability of the die.

TABLE 1 Comparative Example 1 Example 2 Example 1 Resin A1 A1 A1 Firstrelease agent A A A Second release agent A B 13 1 Time 20 Times 1 Time20 Times 1 Time 20 Times Antifouling Antifouling Contact angle of ≥130≥130 ≥130 ≥130 ≥130 ≥130 film properties water (°) Ease of wiping offGood Good Good Good Good Poor Die Releasability Contant angleof >150 >150 >150 >150 148 132 water (°)

Table 1 demonstrates that the antifouling properties of the antifoulingfilm were maintained at high levels and the releasability of the die wasalso maintained at a high level in Examples 1 and 2. In ComparativeExample 1, the antifouling film (20 times) showed impaired ease ofwiping off and the die (20 times) showed a smaller contact angle ofwater. The antifouling film preferably includes a surface that shows acontact angle of 130° or greater with water. The examination was alsoperformed for the case of using a compound containing aperfluoro(poly)ether group with the active component content of 0.5 wt %in the resin. This examination showed the antifouling properties in thiscase were also excellent.

As shown in FIGS. 2 to 4, the degree of increase in the reflectance(“reflectance of antifouling film (20 times)”-“reflectance ofantifouling film (1 time)”) in Examples 1 and 2 was equal to or lowerthan that in Comparative Example 1. This is because the resin (resin A1)constituting the uneven structure was deposited (clogged) on the die (20times) in Comparative Example 1, so that the height of each projectionof the antifouling film (20 times) was lower than that of eachprojection of the antifouling film (1 time).

Therefore, Examples 1 and 2 were found to be capable of long-termcontinuous production of an antifouling film having excellentantifouling properties.

[Evaluation 2: Evaluation on Releasability of Die]

As demonstrated in Evaluation 1, the absence of the second release agentcaused reduction in releasability of the die after long-term continuousformation of the uneven structure using the die. The degree of reductionin releasability of the die was evaluated in the following.

(Evaluation 2-1) Evaluation in Accordance with Type of First ReleaseAgent

The degree of reduction in releasability of the die was evaluated whilethe type of the first release agent was changed.

The materials used for producing the antifouling films were the same asthose in Comparative Example 1, except for the first release agent.

(First Release Agent 5)

The following four compounds were used as the first release agents. Theabbreviations of the respective first release agents are as follows.

(1) “First Release Agent A”

“Optool DSX” (Daikin Industries, Ltd.)

(2) “First Release Agent B”

“Optool UD100” (Daikin Industries, Ltd.)

(3) “First Release Agent C”

Mixture of “Optool DSX” (Daikin Industries, Ltd.) andC₆F₁₃CH₂CH₂Si(OMe)₃ (weight ratio 1:1)

(4) “First Release Agent D”

C₆F₁₃CH₂CH₂Si(OMe)₃

Comparative Examples 2 to 5

An antifouling film of each example was produced in the same manner asin Comparative Example 1, except that the composition was changed asshown in Table 2 and the number of processes repeated was changed.

(Evaluation Contents and Evaluation Results)

For the dies used in Comparative Examples 2 to 5, the releasability wasevaluated. For the releasability, the water repellency (contact angle ofwater) was evaluated in the same manner as in Evaluation 1. The resultsare shown in Table 2.

TABLE 2 Comparative Comparative Comparative Comparative Example 2Example 3 Example 4 Example 5 Resin A1 A1 A1 A1 First release agent A BC D Die Contact  1 Time 148.0 146.7 145.9 121.8 angle of 10 Times 140.1142.8 139.1 — water 20 Times 128.6 135.6 124.2 — (°) 30 Times 116.7125.5 118.3 — 40 Times 109.8 117.2 113.1 — 50 Times — 116.6 — — 60 Times— 116.3 — — 70 Times — 116.3 — — 80 Times — 112.6 — — 90 Times — 114.8 ——

Table 2 demonstrates that the releasability of the die was low and notmaintained for a long period of time in each of Comparative Examples 2to 5 as compared with Examples 1 and 2 (Evaluation 1). In particular, inComparative Example 5, even the die (1 time) showed a small contactangle of water. This is because the first release agent D is aperfluoroalkyl compound, unlike the first release agents A to C.

(Evaluation 2-2) Evaluation in Accordance with Type of Resin

The degree of reduction in releasability of the die was evaluated whilethe type of the resin was changed.

The materials used for producing the antifouling film were the same asthose in Comparative Example 1, except for the resin.

(Resin 3)

The following four resins were used. The abbreviations of the respectiveresins are as follows.

(1) “Resin A2”

The resin A2 was prepared by mixing the following materials.

<Monomer>

-   -   “UA-510H” (Kyoeisha Chemical Co., Ltd.): 8 wt %    -   “ATM-35E” (Shin Nakamura Chemical Co., Ltd.): 46 wt %    -   “Light Acrylate DPE-6A” (Kyoeisha Chemical Co., Ltd.): 19 wt %    -   “DMAA” (KJ Chemicals Corp.): 25 wt %        <Polymerization Initiator>    -   “Irgacure 819” (BASF SE): 2 wt %        (2) “Resin A3”

The resin A3 was prepared by mixing the following materials, and was thesame as the above resin A1.

<Antifouling Agent>

-   -   Antifouling agent A: 12.5 wt %        <Monomer>    -   “UA-510H” (Kyoeisha Chemical Co., Ltd.): 8 wt %    -   “ATM-35E” (Shin Nakamura Chemical Co., Ltd.): 41 wt %    -   “Light Acrylate DPE-6A” (Kyoeisha Chemical Co., Ltd.): 19 wt %    -   “DMAA” (KJ Chemicals Corp.): 17.5 wt %        <Polymerization Initiator>    -   “Irgacure 819” (BASF SE): 2 wt %        (3) “Resin A4”

The resin A4 was prepared by mixing the following materials.

<Antifouling Agent>

-   -   Phosphoric acid ester material: 1 wt %        <Monomer>    -   “UA-510H” (Kyoeisha Chemical Co., Ltd.): 8 wt %    -   “ATM-35E” (Shin Nakamura Chemical Co., Ltd.): 46 wt %    -   “Light Acrylate DPE-6A” (Kyoeisha Chemical Co., Ltd.): 19 wt %    -   “DMAA” (KJ Chemicals Corp.): 24 wt %        <Polymerization Initiator>    -   “Irgacure 819” (BASF SE): 2 wt %        (4) “Resin A5”

The resin A5 was prepared by mixing the following materials.

<Antifouling Agent>

-   -   “Megaface RS-76-NS” (DIC Corp.): 0.25 wt %        <Monomer>    -   “UA-510H” (Kyoeisha Chemical Co., Ltd.): 8 wt %    -   “ATM-35E” (Shin Nakamura Chemical Co., Ltd.): 48 wt %    -   “Light Acrylate DPE-6A” (Kyoeisha Chemical Co., Ltd.): 19 wt %    -   “DMAA” (KJ Chemicals Corp.): 22.75 wt %        <Polymerization Initiator>    -   “Irgacure 819” (BASF SE): 2 wt %

Comparative Examples 6 to 9

An antifouling film of each example was produced in the same manner asin Comparative Example 1, except that the composition was changed asshown in Table 3 and the number of processes repeated was changed.

TABLE 3 Comparative Comparative Comparative Comparative Example 6Example 7 Example 8 Example 9 Resin A2 A3 A4 A5 First release A A A Aagent(Evaluation Contents and Evaluation Results)

For the dies used in Comparative Examples 6 to 9, the releasability wasevaluated. For the releasability, the water repellency (contact angle ofwater) was evaluated in the same manner as in Evaluation 1. The resultsare shown in FIG. 5. FIG. 5 is a graph showing the transition of thecontact angles of water on dies used in Comparative Examples 6 to 9.FIG. 5 shows that the contact angle of water on the surface of the diewas gradually reduced as the number of processes repeated was increasedin each of Comparative Examples 6 to 9. In other words, reduction inreleasability of the die cannot be prevented even though the type of theresin is changed in long-term continuous production of an antifoulingfilm unless the second release agent is used.

Next, in Comparative Example 6, the number of processes repeated wasincreased and the change in the properties of the resulting antifoulingfilm was evaluated. Specifically, the reflectance and the shape (heightof each projection) of the antifouling film were determined. Themeasurement results are shown in Table 4 and FIG. 6. FIG. 6 is a graphshowing the transition of the reflectance of an antifouling film ofComparative Example 6. In Table 4 and FIG. 6, the length of the unevenstructure formed (hereinafter, also referred to as a process length) wasused as an equivalent indicator of the number of processes repeated.Specifically, the process length L (unit: m) means that the unevenstructure was formed for the length L (unit: m) using the die. In otherwords, the longer the process length is, the greater the number ofprocesses repeated is. In Table 4, the Y value means the reflectance ata wavelength of 550 nm. The reflectance was determined in the samemanner as in Evaluation 1.

TABLE 4 Process length (m) 0 20 40 60 80 100 Reflectance Y value (%)0.12 0.12 0.13 0.24 0.54 1.02 Shape Height of 220 195 155 145 130 100projection (nm)

Table 4 and FIG. 6 demonstrate that the reflectance of the antifoulingfilm was increased and the height of each projection was reduced as theprocess length was increased. This is because the resin constituting theuneven structure was deposited (clogged) on the die as the processlength was increased, so that the height of each projection of theantifouling film formed was gradually reduced and the reflectance wasgradually increased. In other words, reduction in properties of theantifouling film cannot be prevented in long-term continuous productionof an antifouling film unless the second release agent is used.

[Additional Remarks]

An aspect of the present invention may be a method for producing anantifouling film including a polymer layer that includes on a surfacethereof an uneven structure provided with multiple projections at apitch not longer than a wavelength of visible light, the methodincluding: Process (1) of applying a resin to a surface of a substrate;Process (2) of applying a second release agent to a surface of a diecoated with a first release agent; Process (3) of pushing the substrateto the surface of the die coated with the second release agent with theresin in between to form the uneven structure on a surface of the resin;and Process (4) of curing the resin including the uneven structure onthe surface thereof to form the polymer layer, the resin containing anantifouling agent that contains a compound containing aperfluoro(poly)ether group, the first release agent containing acompound that contains a perfluoro(poly)ether group, a hydrolyzablegroup, and a Si atom, the second release agent containing a compoundrepresented by the following formula (F):R¹¹¹—(R¹¹²O)_(m)—R¹¹³  (F)wherein R¹¹¹ and R¹¹³ are each individually a fluorine atom or a —OHgroup; R¹¹² is a C₁-C₄ fluorinated alkylene group; and m is an integerof 2 or greater.

This aspect enables long-term continuous production of an antifoulingfilm having excellent antifouling properties.

The antifouling agent may contain a carbon-carbon double bond-containingcompound that is a reaction product of a component (A) and a component(B), the component (A) being a polyisocyanate that is a trimer of adiisocyanate and the component (B) being an active-hydrogen-containingcompound. The component (B) may contain a component (B1) and a component(B2), the component (B1) being an active-hydrogen-containingperfluoropolyether and the component (B2) being a monomer containing acarbon-carbon double bond-containing group and active hydrogen. Thecomponent (B1) may be at least one compound represented by one of thefollowing formulas (B1-i) and (B1-ii). This embodiment allows theantifouling agent to be effectively used.Rf-PFPE¹-Z—X  (B1-i)X—Z-PFPE²-Z—X  (B1-ii)

In the formulas (B1-i) and (B1-ii), Rf is a C₁-C₁₆ alkyl groupoptionally substituted with one or more fluorine atoms;

PFPE¹ is a group represented by the following formula (D1), (D2), or(D3):—(OCF₂CF₂CF₂CF₂)_(b)—  (D1)wherein b is an integer of 1 to 200;—(OCF₂CF₂CF₂CF₂)_(a)—(OCF₂CF₂CF₂CF₂)_(b)—(OCF₂CF₂)_(c)—(OCF₂)_(d)—  (D2)wherein a and b are each individually an integer of 0 to 30; c and d areeach individually an integer of 1 to 200; and the repeating unitsparenthesized with a, b, c, or d are present in any order in the formula(D2); and—(OC₂F₄—R⁵)_(i)—  (D3)wherein R⁵ is OC₂F₄, OC₃F₆, or OC₄F₈; and i is an integer of 2 to 100;

PFPE² is a group represented by the following formula (D4) or (D5):—(OCF₂CF₂CF₂CF₂)_(b)—  (D4)wherein b is an integer of 1 to 200; and(OC₂F₄—R⁵)_(i)—  (D5)wherein R⁵ is OC₂F₄, OC₃F₆, or OC₄F₈; and i is an integer of 2 to 100;

Zs are each individually a divalent organic group; and

X is an active-hydrogen-containing group.

The first release agent may contain at least one compound selected fromthe group consisting of compounds represented by the following formulas(1a), (1b), (2a), (2b), (3a), and (3b). This embodiment allows the firstrelease agent to be effectively used.

In the formulas (1a), (1b), (2a), and (2b), Rf¹ and Rf² are each aC₁-C₁₆ alkyl group optionally substituted with one or more fluorineatoms; a, b, c, and s are each individually an integer of 0 to 200, andthe sum of them is 1 or greater; the repeating units parenthesized witha, b, c, or s are present in any order in the formulas (1a), (1b), (2a),and (2b); d and f are each 0 or 1; e and g are each an integer of 0 to2; h and j are each 1 or 2; i and k are each an integer of 2 to 20; X isa hydrogen atom or a halogen atom; Y is a hydrogen atom or a lower alkylgroup; Z is a fluorine atom or a lower fluoroalkyl group; R¹ and R² areeach a C₁-C₂₂ alkyl group, a C₁-C₂₂ alkoxy group, or a hydroxy group; Tis a hydroxy group or a hydrolyzable group; n is an integer of 1 to 3;and m and l are each an integer of 1 to 10.A-Rf—X-SiQ_(k)Y_(3-k)  (3a)Y_(3-k)Q_(k)Si—X—Rf—X-SiQ_(k)Y_(3-k)  (3b)

In the formulas (3a) and (3b), A is a C1-C16 alkyl group optionallysubstituted with one or more fluorine atoms; Rf is a group representedby the following formula (E1):—(OC₄F₈)_(a)—(OC₃F₆)_(b)—(OC₂F₄)_(c)—(OCF₂)_(d)—  (E1)wherein a, b, c, and d are each individually an integer of 0 or greater,and the sum of them is 1 or greater; and the repeating unitsparenthesized with a, b, c, or d are present in any order in the formula(E1);

X is a divalent organic group; Y is a hydroxy group, a hydrolyzablegroup, or a hydrocarbon group; Q is a group represented by the followingformula (E2):—Z—SiR¹ _(n)R² _(3-n)  (E2)wherein Zs are each individually a divalent organic group; R's are eachindividually a hydroxy group or a hydrolyzable group; R²s are eachindividually a C1-C22 alkyl group or Q′; Q′ is defined in the samemanner as Q; and each n in Q and Q′ is individually an integer of 0 to3, and the sum of them is 1 or greater; and

k is an integer of 1 to 3.

The resin may contain 0.1 wt % or more and 10 wt % or less of an activecomponent of the antifouling agent. This embodiment can sufficientlyimprove the antifouling properties and rubbing resistance of theantifouling film.

The resin may be curable by ultraviolet rays. This embodiment allows theresin to be effectively used.

The antifouling film may include a surface that shows a contact angle of130° or greater with water. This embodiment can sufficiently improve theantifouling properties of the antifouling film.

The polymer layer may have a thickness of 1 μm or greater and 20 μm orsmaller. This embodiment can prevent easy sighting of defects (e.g.,deformation transferred from the die, foreign substances) in theantifouling film. This embodiment can also prevent occurrence of defectssuch as curling of the antifouling film due to curing and shrinkage ofthe resin.

The pitch may be 20 nm or greater and 400 nm or smaller. This embodimentcan prevent reduction in rubbing resistance of the antifouling film andcan prevent occurrence of undesirable appearance of the antifoulingfilm.

Each of the projections may have a height of 50 nm or greater and 500 nmor smaller. This embodiment can prevent insufficient antireflectiveperformance of the antifouling film. This embodiment can also preventinsufficient mechanical strength of the projections and thus can preventreduction in rubbing resistance of the antifouling film.

Each of the projections may have an aspect ratio of 0.13 or greater and25 or smaller. This embodiment enables both mechanical strength (rubbingresistance) and optical performance (antireflective performance,performance of preventing unnecessary phenomena such as diffraction andscattering) of the antifouling film at high levels.

REFERENCE SIGNS LIST

-   1: antifouling film-   2: substrate-   3: resin-   4: die-   5: first release agent-   6: polymer layer-   7: projection-   8: second release agent-   P: pitch-   Q: thickness of polymer layer

The invention claimed is:
 1. A method for producing an antifouling filmincluding a polymer layer that includes on a surface thereof an unevenstructure provided with multiple projections at a pitch not longer thana wavelength of visible light, the method comprising: Process (1) ofapplying a resin to a surface of a substrate; Process (2) of applying asecond release agent to a surface of a die coated with a first releaseagent; Process (3) of pushing the substrate to the surface of the diecoated with the second release agent with the resin in between to formthe uneven structure on a surface of the resin; and Process (4) ofcuring the resin including the uneven structure on the surface thereofto form the polymer layer, the resin containing an antifouling agentthat contains a compound containing a perfluoro(poly)ether group, thefirst release agent containing a compound that contains aperfluoro(poly)ether group, a hydrolyzable group, and a Si atom, thesecond release agent containing a compound represented by the followingformula (F):R¹¹¹—(R¹¹²O)_(m)—R¹¹³  (F) wherein R¹¹¹ and R¹¹³ are each individually afluorine atom or a —OH group; R¹¹² is a C1-C4 fluorinated alkylenegroup; and m is an integer of 2 or greater.
 2. The method for producingan antifouling film according to claim 1, wherein the antifouling agentcontains a carbon-carbon double bond-containing compound that is areaction product of a component (A) and a component (B), the component(A) being a polyisocyanate that is a trimer of a diisocyanate and thecomponent (B) being an active-hydrogen-containing compound, thecomponent (B) contains a component (B1) and a component (B2), thecomponent (B1) being an active-hydrogen-containing perfluoropolyetherand the component (B2) being a monomer containing a carbon-carbon doublebond-containing group and active hydrogen, the component (B1) is atleast one compound represented by one of the following formulas (B1-i)and (B1-ii):Rf-PFPE¹-Z—X  (B1-i)X—Z-PFPE²-Z—X  (B1-ii) wherein Rf is a C1-C16 alkyl group optionallysubstituted with one or more fluorine atoms; PFPE¹ is a grouprepresented by the following formula (D1), (D2), or (D3):—(OCF₂CF₂CF₂CF₂)_(b)—  (D1) wherein b is an integer of 1 to 200;—(OCF₂CF₂CF₂CF₂)_(a)—(OCF₂CF₂CF₂CF₂)_(b)—(OCF₂CF₂)_(c)—(OCF₂)_(d)—  (D2)wherein a and b are each individually an integer of 0 to 30; c and d areeach individually an integer of 1 to 200; and the repeating unitsparenthesized with a, b, c, or d are present in any order in the formula(D2); and—(OC₂F₄—R⁵)_(i)—  (D3) wherein R⁵ is OC₂F₄, OC₃F₆, or OC₄F₈; and i is aninteger of 2 to 100; PFPE² is a group represented by the followingformula (D4) or (D5):—(OCF₂CF₂CF₂CF₂)_(b)—  (D4) wherein b is an integer of 1 to 200; and—(OC₂F₄—R⁵)_(i)—  (D5) wherein R⁵ is OC₂F₄, OC₃F₆, or OC₄F₈; and i is aninteger of 2 to 100; Zs are each individually a divalent organic group;and X is an active-hydrogen-containing group.
 3. The method forproducing an antifouling film according to claim 1, wherein the resincontains 0.1 wt % or more and 10 wt % or less of an active component ofthe antifouling agent.
 4. The method for producing an antifouling filmaccording to claim 1, wherein the resin is curable by ultraviolet rays.5. The method for producing an antifouling film according to claim 1,wherein the antifouling film includes a surface that shows a contactangle of 130° or greater with water.
 6. The method for producing anantifouling film according to claim 1, wherein the polymer layer has athickness of 1 μm or greater and 20 μm or smaller.
 7. The method forproducing an antifouling film according to claim 1, wherein the pitch is20 nm or greater and 400 nm or smaller.
 8. The method for producing anantifouling film according to claim 1, wherein each of the projectionshas a height of 50 nm or greater and 500 nm or smaller.
 9. The methodfor producing an antifouling film according to claim 1, wherein each ofthe projections has an aspect ratio of 0.13 or greater and 25 orsmaller.
 10. The method for producing an antifouling film according toclaim 1, wherein the second release agent contains a repeating unit of—(CF₂CF₂CF₂O)—.